Publications

@article{nokey,

title = {Postsynthetic Transformation of Imine- into Nitrone-Linked Covalent Organic Frameworks for Atmospheric Water Harvesting at Decreased Humidity},

author = {L Grunenberg and G Savasci and S T Emmerling and F Heck and S Bette and A Cima Bergesch and C Ochsenfeld and B V Lotsch},

url = {https://doi.org/10.1021/jacs.3c02572},

doi = {10.1021/jacs.3c02572},

issn = {0002-7863},

year  = {2023},

date = {2023-05-25},

journal = {Journal of the American Chemical Society},

volume = {145},

number = {24},

pages = {13241-13248},

abstract = {Herein, we report a facile postsynthetic linkage conversion method giving synthetic access to nitrone-linked covalent organic frameworks (COFs) from imine- and amine-linked COFs. The new two-dimensional (2D) nitrone-linked covalent organic frameworks, NO-PI-3-COF and NO-TTI-COF, are obtained with high crystallinity and large surface areas. Nitrone-modified pore channels induce condensation of water vapor at 20% lower humidity compared to their amine- or imine-linked precursor COFs. Thus, the topochemical transformation to nitrone linkages constitutes an attractive approach to postsynthetically fine-tune water adsorption properties in framework materials.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Optical Properties of Slot-Die Coated Hybrid Colloid/Cellulose-Nanofibril Thin Films},

author = {C Harder and A E Alexakis and Y Bulut and S Xiong and B Sochor and G Pan and H Zhong and K Goordeyeva and M A Reus and V K\"{o}rstgens and A Jeromin and T F Keller and L D S\"{o}derberg and E Malmstr\"{o}m and P M\"{u}ller-Buschbaum and S V Roth},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202203058},

doi = {https://doi.org/10.1002/adom.202203058},

issn = {2195-1071},

year  = {2023},

date = {2023-04-05},

journal = {Advanced Optical Materials},

volume = {n/a},

number = {n/a},

pages = {2203058},

abstract = {Abstract Correlating nanostructure and optical properties of thin hybrid films is the crucial ingredient for designing sustainable applications ranging from structural colors in anticounterfeiting to sensors. Here, the tailoring of the refractive index of hybrid cellulose nanofibril/water-dispersed colloidal ink thin films is presented. The authors apply scalable, layer-by-layer slot-die coating for preparing the cellulose nanofibril and hybrid thin films. Making use of the mobility of the polymer chains in the colloids upon annealing, the influence of the different colloid sizes and their glass transition temperature on the refractive index of the hybrid material is shown. The complex refractive indices of the thin films are characterized by spectroscopic ellipsometry and correlated to the different nanostructures of the thin films. The authors find that post-deposition annealing changes the colloidal nanostructure from particulate to agglomerates. Depending on the size of the colloids, imbibition of the colloids into the cellulose nanofibril template is observed. This scalable approach offers new avenues in structural color functional biomaterial hybrid layers.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {On-surface synthesis of enetriynes},

author = {N Cao and B Yang and A Riss and J Rosen and J Bj\"{o}rk and J V Barth},

url = {https://doi.org/10.1038/s41467-023-36828-y},

doi = {10.1038/s41467-023-36828-y},

issn = {2041-1723},

year  = {2023},

date = {2023-03-06},

journal = {Nature Communications},

volume = {14},

number = {1},

pages = {1255},

abstract = {Belonging to the enyne family, enetriynes comprise a distinct electron-rich all-carbon bonding scheme. However, the lack of convenient synthesis protocols limits the associated application potential within, e.g., biochemistry and materials science. Herein we introduce a pathway for highly selective enetriyne formation via tetramerization of terminal alkynes on a Ag(100) surface. Taking advantage of a directing hydroxyl group, we steer molecular assembly and reaction processes on square lattices. Induced by O2 exposure the terminal alkyne moieties deprotonate and organometallic bis-acetylide dimer arrays evolve. Upon subsequent thermal annealing tetrameric enetriyne-bridged compounds are generated in high yield, readily self-assembling into regular networks. We combine high-resolution scanning probe microscopy, X-ray photoelectron spectroscopy and density functional theory calculations to examine the structural features, bonding characteristics and the underlying reaction mechanism. Our study introduces an integrated strategy for the precise fabrication of functional enetriyne species, thus providing access to a distinct class of highly conjugated π-system compounds.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Fully Methylammonium-Free Stable Formamidinium Lead Iodide Perovskite Solar Cells Processed under Humid Air Conditions},

author = {K Wang and J Huo and L Cao and P Yang and P M\"{u}ller-Buschbaum and Y Tong and H Wang},

url = {https://doi.org/10.1021/acsami.2c23134},

doi = {10.1021/acsami.2c23134},

issn = {1944-8244},

year  = {2023},

date = {2023-02-28},

journal = {ACS Applied Materials \& Interfaces},

volume = {15},

number = {10},

pages = {13353-13362},

abstract = {Fabricating perovskite solar cells (PSCs) in ambient air condition is beneficial for lowering the processing cost and boosting the commercialization. Formamidinium lead iodide (FAPbI3) is an attractive candidate for efficient PSCs; however, it easily suffers from degradation and phase transition in the presence of ambient moisture. Methylammonium (MA) cation is commonly incorporated to stabilize FAPbI3, whereas the residual MA tends to deteriorate the thermal and operational stability. Herein, we report a MA-free strategy to fabricate high-quality α-FAPbI3 films and inverted PSCs under open air conditions with a relative humidity (RH) of 60 ± 10%. The incorporation of phenylethylammonium iodide (PEAI) effectively inhibits the decomposition and phase transition of FAPbI3 during its crystallization in humid air. Accordingly, phase-pure α-FAPbI3 perovskite films with significantly reduced δ-FAPbI3 and PbI2 content are successfully obtained. In addition, introducing PEAI strongly enhances the crystallinity of FAPbI3 perovskite films, thereby yielding enlarged grain sizes and reduced grain boundaries. Defects at the grain boundaries and surface are further passivated by PEAI addition, so that the trap state density is significantly decreased. As a result, the non-radiative recombination is effectively suppressed and the charge carrier transport is promoted. The inverted device optimized with a suitable PEAI concentration exhibits an enhanced power conversion efficiency (PCE) of 17.83%, which significantly surpasses the control device (12.29% PCE). Moreover, the PEAI optimized FAPbI3 PSCs demonstrate strongly improved long-term stability, with nearly 97% PCE maintained after 27-day storage under ambient conditions. This work provides a feasible way to fabricate PSCs in ambient air for promoting their wide range of applications.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electrically Conductive Carbazole and Thienoisoindigo-Based COFs Showing Fast and Stable Electrochromism},

author = {K Muggli and L Spies and D Bessinger and F Auras and T Bein},

url = {https://doi.org/10.1021/acsnanoscienceau.2c00049},

doi = {10.1021/acsnanoscienceau.2c00049},

year  = {2023},

date = {2023-02-17},

journal = {ACS Nanoscience Au},

abstract = {Thienothiophene thienoisoindigo (ttTII)-based covalent organic frameworks (COFs) have been shown to offer low band gaps and intriguing optical and electrochromic properties. So far, only one tetragonal thienothiophene thienoisoindigo-based COF has been reported showing stable and fast electrochromism and good coloration efficiencies. We have developed two novel COFs using this versatile and nearly linear ttTII building block in a tetragonal and a hexagonal framework geometry to demonstrate their attractive features for optoelectronic applications of thienoisoindigo-based COFs. Both COFs exhibit good electrical conductivities, show promising optical absorption features, are redox-active, and exhibit a strong electrochromic behavior when applying an external electrical stimulus, shifting the optical absorption even farther into the NIR region of the electromagnetic spectrum and achieving absorbance changes of up to 2.5 OD. Cycle-stable cyclic voltammograms with distinct oxidation and reduction waves reveal excellent reversibility and electrochromic switching over 200 cycles and confirm the high stability of the frameworks. Furthermore, high coloration efficiencies in the NIR region and fast switching speeds for coloration/decoloration as fast as 0.75 s/0.37 s for the Cz-ttTII COF and 0.61 s/0.29 s for the TAPB-ttTII COF at 550 nm excitation were observed, outperforming many known electrochromic materials, and offering options for a great variety of applications, such as stimuli-responsive coatings, optical information processing, or thermal control.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Photocatalytic CO2-to-Syngas Evolution with Molecular Catalyst Metal-Organic Framework Nanozymes},

author = {P M Stanley and A Y Su and V Ramm and P Fink and C Kimna and O Lieleg and M Elsner and J A Lercher and B Rieger and J Warnan and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202207380},

doi = {https://doi.org/10.1002/adma.202207380},

issn = {0935-9648},

year  = {2023},

date = {2023-02-01},

journal = {Advanced Materials},

volume = {35},

number = {6},

pages = {2207380},

abstract = {Abstract Syngas, a mixture of CO and H2, is a high-priority intermediate for producing several commodity chemicals, e.g., ammonia, methanol, and synthetic hydrocarbon fuels. Accordingly, parallel sunlight-driven catalytic conversion of CO2 and protons to syngas is a key step toward a sustainable energy cycle. State-of-the-art catalytic systems and materials often fall short as application-oriented concurrent CO and H2 evolution requires challenging reaction conditions which can hamper stability, selectivity, and efficiency. Here a light-harvesting metal-organic framework hosting two molecular catalysts is engineered to yield colloidal, water-stable, versatile nanoreactors for photocatalytic syngas generation with highly controllable product ratios. In-depth fluorescence, X-ray, and microscopic studies paired with kinetic analysis show that the host delivers energy efficiently to active sites, conceptually yielding nanozymes. This unlocked sustained CO2 reduction and H2 evolution with benchmark turnover numbers and record incident photon conversions up to 36%, showcasing a highly active and durable all-in-one material toward application in solar energy-driven syngas generation.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ligand Chemistry of Inorganic Lead Halide Perovskite Nanocrystals},

author = {N Fiuza-Maneiro and K Sun and I L\'{o}pez-Fern\'{a}ndez and S G\'{o}mez-Gra\~{n}a and P M\"{u}ller-Buschbaum and L Polavarapu},

url = {https://doi.org/10.1021/acsenergylett.2c02363},

doi = {10.1021/acsenergylett.2c02363},

year  = {2023},

date = {2023-01-26},

journal = {ACS Energy Letters},

pages = {1152-1191},

abstract = {Lead halide perovskite nanocrystals (LHP NCs) have emerged as next-generation semiconductor materials with outstanding optical and optoelectronic properties. Because of the high surface-to-volume ratio, the optical and optoelectronic performance and the colloidal stability of LHP NCs largely depend on their surface chemistry, especially the ligands and surface termination. On one hand, the capping ligands improve the colloidal stability and luminescence; on the other hand the highly dynamic binding nature of ligands is detrimental to the colloidal stability and photoluminescence of LHP NCs. In addition, the surface functionalization with desired molecules induces new functionalities such as chirality, light harvesting, and triplet sensitization through energy/electron transfer or use as X-ray detectors. In this review, we present the current understanding of an atomic view of the surface chemistry of colloidal LHP NCs, including crystal termination, vacancies, and different types of capping ligands. Furthermore, we discuss the ligand-induced functionalities, including photocatalysis and chirality.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Shrinking gate fluorescence correlation spectroscopy yields equilibrium constants and separates photophysics from structural dynamics},

author = {T Schr\"{o}der and J Bohlen and S E Ochmann and P Sch\"{u}ler and S Krause and D C Lamb and P Tinnefeld},

url = {https://www.pnas.org/doi/abs/10.1073/pnas.2211896120},

doi = {doi:10.1073/pnas.2211896120},

year  = {2023},

date = {2023-01-18},

journal = {Proceedings of the National Academy of Sciences},

volume = {120},

number = {4},

pages = {e2211896120},

abstract = {Fluorescence correlation spectroscopy is a versatile tool for studying fast conformational changes of biomolecules especially when combined with F\"{o}rster resonance energy transfer (FRET). Despite the many methods available for identifying structural dynamics in FRET experiments, the determination of the forward and backward transition rate constants and thereby also the equilibrium constant is difficult when two intensity levels are involved. Here, we combine intensity correlation analysis with fluorescence lifetime information by including only a subset of photons in the autocorrelation analysis based on their arrival time with respect to the excitation pulse (microtime). By fitting the correlation amplitude as a function of microtime gate, the transition rate constants from two fluorescence-intensity level systems and the corresponding equilibrium constants are obtained. This shrinking-gate fluorescence correlation spectroscopy (sg-FCS) approach is demonstrated using simulations and with a DNA origami-based model system in experiments on immobilized and freely diffusing molecules. We further show that sg-FCS can distinguish photophysics from dynamic intensity changes even if a dark quencher, in this case graphene, is involved. Finally, we unravel the mechanism of a FRET-based membrane charge sensor indicating the broad potential of the method. With sg-FCS, we present an algorithm that does not require prior knowledge and is therefore easily implemented when an autocorrelation analysis is carried out on time-correlated single-photon data.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {The neglected influence of zinc oxide light-soaking on stability measurements of inverted organic solar cells},

author = {M G\"{u}nther and S Lotfi and S S Rivas and D Bl\"{a}tte and J P Hofmann and T Bein and T Ameri},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202209768},

doi = {https://doi.org/10.1002/adfm.202209768},

issn = {1616-301X},

year  = {2023},

date = {2023-01-15},

journal = {Advanced Functional Materials},

volume = {33},

number = {13},

pages = {2209768},

abstract = {Abstract Although zinc oxide (ZnO) is one of the most commonly used materials for electron transport layers in organic solar cells (OSCs), it also comes with disadvantages such as the so-called light-soaking issues, i.e., its need for exposure to UV light to reach its full potential in OSCs. Here, the impact of ZnO light-soaking issues on stability measurements of OSCs is investigated. It is found that in the absence of UV light a reversible degradation occurs, which is independent of the used active layer material and accelerates at higher temperatures but can be undone with a short UV exposure. This reversible aging is attributed to the re-adsorption of oxygen, which for manufacturing reasons is trapped at the interface of ZnO, even in an oxygen-free environment. This oxygen can be removed with a UV pretreatment of the ZnO but at the expense of device efficiency and production that has to take place in an oxygen-free environment. This study establishes that stability measurements of ZnO-containing OSCs must be performed exclusively with a light source including a UV part since the usage of a simple white light source \textendash as often reported in the literature \textendash can lead to erroneous results.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Film Formation Kinetics of Polymer Donor and Nonfullerene Acceptor Active Layers During Printing Out of 1,2,4-Trimethylbenzene in Ambient Conditions},

author = {X Jiang and S Grott and V K\"{o}rstgens and K S Wienhold and Z Li and J Zhang and C R Everett and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/solr.202201077},

doi = {https://doi.org/10.1002/solr.202201077},

issn = {2367-198X},

year  = {2023},

date = {2023-01-13},

journal = {Solar RRL},

volume = {7},

number = {6},

pages = {2201077},

abstract = {Slot-die coating is a promising upscaling fabrication method to promote commercialization in the field of organic solar cells. Herein, the nonfullerene active layer blend of a conjugated polymer PffBT4T-2OD and a small molecule acceptor EH-IDTBR, which is printed out of the nonhalogenated solvent 1,2,4-trimethylbenzene, is studied. The film formation kinetics of the active layer PffBT4T-2OD:EH-IDTBR is probed in terms of the temporal evolutions in morphology as well as molecular conformation and aggregation as revealed by in situ grazing-incidence small angle X-ray scattering and UV\textendashvis spectroscopy during the film printing process. A five-regime mesoscale domain growth process is observed in the active layer from the liquid state to the final dry state. The solvent evaporation-induced domain growth is accompanied with molecular stacking in a distinct J-type aggregation of the acceptor and a slight H-type aggregation of the donor molecules. The printed active layers exhibit an edge-on dominated PffBT4T-2OD and a face-on dominated EH-IDTBR crystallite structure. Compared to the neat PffBT4T-2OD and EH-IDTBR films, in the active layer, the crystallite structure deviates slightly in lattice spacing.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Covalent Organic Framework Thin-Film Photodetectors from Solution-Processable Porous Nanospheres},

author = {S Bag and H S Sasmal and S P Chaudhary and K Dey and D Bl\"{a}tte and R Guntermann and Y Zhang and M Polo\v{z}ij and A Kuc and A Shelke and R K Vijayaraghavan and T G Ajithkumar and S Bhattacharyya and T Heine and T Bein and R Banerjee},

url = {https://doi.org/10.1021/jacs.2c09838},

doi = {10.1021/jacs.2c09838},

issn = {0002-7863},

year  = {2023},

date = {2023-01-09},

journal = {Journal of the American Chemical Society},

volume = {145},

number = {3},

pages = {1649-1659},

abstract = {The synthesis of homogeneous covalent organic framework (COF) thin films on a desired substrate with decent crystallinity, porosity, and uniform thickness has great potential for optoelectronic applications. We have used a solution-processable sphere transmutation process to synthesize 300 ± 20 nm uniform COF thin films on a 2 × 2 cm2 TiO2-coated fluorine-doped tin oxide (FTO) surface. This process controls the nucleation of COF crystallites and molecular morphology that helps the nanospheres to arrange periodically to form homogeneous COF thin films. We have synthesized four COF thin films (TpDPP, TpEtBt, TpTab, and TpTta) with different functional backbones. In a close agreement between the experiment and density functional theory, the TpEtBr COF film showed the lowest optical band gap (2.26 eV) and highest excited-state lifetime (8.52 ns) among all four COF films. Hence, the TpEtBr COF film can participate in efficient charge generation and separation. We constructed optoelectronic devices having a glass/FTO/TiO2/COF-film/Au architecture, which serves as a model system to study the optoelectronic charge transport properties of COF thin films under dark and illuminated conditions. Visible light with a calibrated intensity of 100 mW cm\textendash2 was used for the excitation of COF thin films. All of the COF thin films exhibit significant photocurrent after illumination with visible light in comparison to the dark. Hence, all of the COF films behave as good photoactive substrates with minimal pinhole defects. The fabricated out-of-plane photodetector device based on the TpEtBr COF thin film exhibits high photocurrent density (2.65 ± 0.24 mA cm\textendash2 at 0.5 V) and hole mobility (8.15 ± 0.64 ×10\textendash3 cm2 V\textendash1 S\textendash1) compared to other as-synthesized films, indicating the best photoactive characteristics.},

keywords = {Foundry Organic, Molecularly-Functionalized, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Gold Nanorod DNA Origami Antennas for 3 Orders of Magnitude Fluorescence Enhancement in NIR},

author = {K Trofymchuk and K Ko\l\k{a}taj and V Glembockyte and F Zhu and G P Acuna and T Liedl and P Tinnefeld},

url = {https://doi.org/10.1021/acsnano.2c09577},

doi = {10.1021/acsnano.2c09577},

issn = {1936-0851},

year  = {2023},

date = {2023-01-03},

journal = {ACS Nano},

volume = {17},

number = {2},

pages = {1327-1334},

abstract = {DNA origami has taken a leading position in organizing materials at the nanoscale for various applications such as manipulation of light by exploiting plasmonic nanoparticles. We here present the arrangement of gold nanorods in a plasmonic nanoantenna dimer enabling up to 1600-fold fluorescence enhancement of a conventional near-infrared (NIR) dye positioned at the plasmonic hotspot between the nanorods. Transmission electron microscopy, dark-field spectroscopy, and fluorescence analysis together with numerical simulations give us insights on the heterogeneity of the observed enhancement values. The size of our hotspot region is ∼12 nm, granted by using the recently introduced design of NAnoantenna with Cleared HotSpot (NACHOS), which provides enough space for placing of tailored bioassays. Additionally, the possibility to synthesize nanoantennas in solution might allow for production upscaling.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Control of the Crystallization and Phase Separation Kinetics in Sequential Blade-Coated Organic Solar Cells by Optimizing the Upper Layer Processing Solvent},

author = {Y Wang and J Xue and H Zhong and C R Everett and X Jiang and M A Reus and A Chumakov and S V Roth and M A Adedeji and N Jili and K Zhou and G Lu and Z Tang and G T Mola and P M\"{u}ller-Buschbaum and W Ma},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202203496},

doi = {https://doi.org/10.1002/aenm.202203496},

issn = {1614-6832},

year  = {2023},

date = {2023-01-01},

journal = {Advanced Energy Materials},

volume = {n/a},

number = {n/a},

pages = {2203496},

abstract = {Abstract Sequential deposition of the active layer in organic solar cells (OSCs) is favorable to circumvent the existing drawbacks associated with controlling the microstructure in bulk-heterojunction (BHJ) device fabrication. However, how the processing solvents impact on the morphology during sequential deposition processes is still poorly understood. Herein, high-efficiency OSCs are fabricated by a sequential blade coating (SBC) through optimization of the morphology evolution process induced by processing solvents. It is demonstrated that the device performance is highly dependent on the processing solvent of the upper layer. In situ morphology characterizations reveal that an obvious liquid\textendashsolid phase separation can be identified during the chlorobenzene processing of the D18 layer, corresponding to larger phase separation. During chloroform (CF) processing of the D18 layer, a proper aggregation rate of Y6 and favorable intermixing of lower and upper layers results in the enhanced crystallinity of the acceptor. This facilitates efficient exciton dissociation and charge transport with an inhibited charge recombination in the D18/CF-based devices, contributing to a superior performance of 17.23%. These results highlight the importance of the processing solvent for the upper layer in the SBC strategy and suggest the great potential of achieving optimized morphology and high-efficiency OSCs using the SBC strategy.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Waterborne conductive carbon paste with an eco-friendly binder},

author = {M Shadabfar and M Ehsani and H A Khonakdar and M Abdouss and T Ameri},

url = {https://doi.org/10.1007/s10570-022-04998-5},

doi = {10.1007/s10570-022-04998-5},

issn = {1572-882X},

year  = {2022},

date = {2022-12-22},

journal = {Cellulose},

abstract = {Conductive carbon pastes are widely used in flexible and printed electronic devices such as wearable electronics and optoelectronics. The use of conductive pastes comes with some challenges, such as replacing toxic synthetic materials with environmentally-friendly and sustainable ones, achieving an appropriate level of electrical conductivity, and controlling the thickness of the coated film. Waterborne conductive carbon pastes have been used to tackle the mentioned problems. In this study, carboxymethyl cellulose (CMC) was introduced as an eco-friendly binder combined with Graphene Nanoplatelets (GNPs) and Carbon Nanotubes (CNTs) to synthesize a conductive carbon paste without any metallic elements. The double-coated GNP/CNT/CMC paste films were coated on a paper surface using the doctor blade method. Morphological and thermal characteristics, sheet resistance, and optoelectrical properties of the paste films were comprehensively investigated. It was found that the conductive carbon paste containing 35 wt% CNTs exhibits higher conductivity (80.4 S/m) than the other combinations. Moreover, Field Emission Scanning Electron Microscopy (FE-SEM) showed that GNPs and CNTs are distributed within cellulosic matrix very homogeneously. Great flexibility and high electrical conductivity are achieved in the paste film. EIS results implied that the double-coated paste could act as a highly conductive surface in fabricating electrochemical sensors with high performance. In conclusion, this study represents a novel and environmentally-friendly method to produce low-cost, highly-efficient, and large-scale conductive carbon paste.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Antisolvent Additive Engineering for Boosting Performance and Stability of Graded Heterojunction Perovskite Solar Cells Using Amide-Functionalized Graphene Quantum Dots},

author = {E Khorshidi and B Rezaei and A Kavousighahfarokhi and J Hanisch and M A Reus and P M\"{u}ller-Buschbaum and T Ameri},

url = {https://doi.org/10.1021/acsami.2c12944},

doi = {10.1021/acsami.2c12944},

issn = {1944-8244},

year  = {2022},

date = {2022-11-29},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

number = {49},

pages = {54623-54634},

abstract = {Additive and antisolvent engineering strategies are outstandingly efficient in enhancing perovskite quality, photovoltaic performance, and stability of perovskite solar cells (PSCs). In this work, an effective approach is applied by coupling the antisolvent mixture and multi-functional additive procedures, which is recognized as antisolvent additive engineering (AAE). The graphene quantum dots functionalized with amide (AGQDs), which consists of carbonyl, amine, and long hydrophobic alkyl chain functional groups, are added to the antisolvent mixture of toluene (T) and hexane (H) as an efficient additive to form the CH3NH3PbI3 (MAPI):AGQDs graded heterojunction structure. A broad range of analytical techniques, including scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, space charge limited current, UV\textendashvisible spectroscopy, external quantum efficiency, and time-of-flight secondary ion mass spectrometry, are used to investigate the effect of AAE treatment with AGQDs on the quality of perovskite film and performance of the PSCs. Importantly, not only a uniform and dense perovskite film with hydrophobic property is obtained but also defects on the perovskite surface are significantly passivated by the interaction between AGQDs and uncoordinated Pb2+. As a result, an enhanced power conversion efficiency (PCE) of 19.10% is achieved for the champion PSCs treated with AGQD additive, compared to the PCE of 16.00% for untreated reference PSCs. In addition, the high-efficiency PSCs based on AGQDs show high stability and maintain 89% of their initial PCE after 960 h in ambient conditions.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Improvement of the thermoelectric properties of PEDOT:PSS films via DMSO addition and DMSO/salt post-treatment resolved from a fundamental view},

author = {S Tu and T Tian and A Lena Oechsle and S Yin and X Jiang and W Cao and N Li and M A Scheel and L K Reb and S Hou and A S Bandarenka and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://www.sciencedirect.com/science/article/pii/S1385894721038742},

doi = {https://doi.org/10.1016/j.cej.2021.132295},

issn = {1385-8947},

year  = {2022},

date = {2022-09-06},

urldate = {2022-09-06},

journal = {Chemical Engineering Journal},

volume = {429},

pages = {132295},

abstract = {The combination of dimethyl sulfoxide (DMSO)-solvent doping and physical\textendashchemical DMSO/salt de-doping in a sequence has been used to improve the thermoelectric (TE) properties of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films. A high power factor of ca.105.2 µW m−1 K−2 has been achieved for the PEDOT:PSS film after post-treatment with 10 % sodium sulfite (Na2SO3) in the DMSO/salt mixture (v/v), outperforming sodium bicarbonate (NaHCO3). The initial DMSO-doping treatment induces a distinct phase separation by facilitating the aggregation of the PEDOT molecules. At the same time, the subsequent DMSO/salt de-doping post-treatment strengthens the selective removal of the surplus non-conductive PSS chains. Substantial alterations in the oxidation level, chain conformations, PEDOT crystallites and their preferential orientation are observed upon treatment on the molecular level. At the mesoscale level, the purification and densification of PEDOT-rich domains enable the realization of inter-grain coupling by the formation of the electronically well-percolated network. Thereby, both electrical conductivity and Seebeck coefficient are optimized.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {The Puzzling Question about the Origin of the Second Electron in the Molecular Photocatalytic Reduction of CO2},

author = {C Thomas and M Wittig and B Rieger},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cctc.202200841},

doi = {https://doi.org/10.1002/cctc.202200841},

issn = {1867-3880},

year  = {2022},

date = {2022-09-04},

journal = {ChemCatChem},

volume = {14},

number = {21},

pages = {e202200841},

abstract = {Abstract Herein, a new supramolecular photocatalyst RuRe3 containing three Re(dmb)CO3Cl (dmb=4,4‘-dimethyl-2,2‘-bipyridine) (Re) building blocks connected through an ethylene bridge to one [Ru(dmb)3]2+-unit (Ru) is presented. We investigated the photophysical properties of this novel tetranuclear complex and compared these to compounds with one (RuRe) and two (RuRe2) catalytic units. Under irradiation, all three photocatalysts exhibit high activity and photostability for the reduction of CO2 to CO, with RuRe3 achieving the highest turnover number (11800) reported to date for a Re(I)/Ru(II)-containing homogeneous catalyst. This tetranuclear complex is especially superior at small catalyst concentrations, which is attributed to an efficient second electron transfer via an intramolecular mechanism. Intermolecular electron transfer from small and mobile Re to RuRe motifs are found to also increase the catalytic performance of the system to a similar level (turnover number=12100). These synergistic effects are attributed to an improved catalytic cycle, stabilizing the bi- and tetrametallic complexes by providing the electrons quickly and effectively. Since the second electron provision is not finally clarified for molecular systems until today, our photocatalytic studies present important insights into this crucial step. Further, these investigations should be considered for the design and synthesis of new and efficient supramolecular CO2-reducing photocatalysts.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Oriented Thiophene-Extended Benzotrithiophene Covalent Organic Framework Thin Films: Directional Electrical Conductivity},

author = {L Frey and J F P\"{o}hls and M Hennemann and A M\"{a}hringer and S Reuter and T Clark and R T Weitz and D D Medina},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202205949},

doi = {https://doi.org/10.1002/adfm.202205949},

issn = {1616-301X},

year  = {2022},

date = {2022-08-24},

journal = {Advanced Functional Materials},

volume = {n/a},

number = {n/a},

pages = {2205949},

abstract = {Abstract The synthesis of covalent organic frameworks (COFs) based on a novel thiophene-extended benzotrithiophene (BTT) building block is described, which in combination with triazine-based amines (1,3,5-triazine-2,4,6-triyl)trianiline (TTA) or (1,3,5-triazine-2,4,6-triyl)tris(([1,1´-biphenyl]-4-amine)) (TTTBA)) affords crystalline, and porous imine-linked COFs, BTT TTA and BTT TTTBA, with surface areas as high as 932 and 1200 m2 g−1, respectively. Oriented thin films are grown successfully on different substrates, as indicated by grazing incidence diffraction (GID). Room-temperature in-plane electrical conductivity of up to 10−4 S m−1 is measured for both COFs. Temperature-dependent electrical conductivity measurements indicate activation energies of ≈123.3 meV for BTT TTA and ≈137.5 meV for BTT TTTBA and trap-dominated charge transport via a hopping mechanism for both COFs. Moreover, conductive atomic force microscopy reveals directional and defect-dominated charge transport in the oriented BTT COF films with a strong preference for the in-plane direction within the molecular 2D-planes. Quantum mechanical calculations predict BTT TTTBA to conduct holes and electrons effectively in both in-plane and out-of-plane directions. In-plane, charge carrier transport is of hopping character where the triazine cores represent the barrier. Out-of-plane, a continuous charge-carrier pathway is calculated that is hampered by an imposed structural defect simulated by a rotated molecular COF layer.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Revealing and Controlling Energy Barriers and Valleys at Grain Boundaries in Ultrathin Organic Films},

author = {L S Walter and A Axt and J W Borchert and T Kammerbauer and F Winterer and J Lenz and S L Weber and R T Weitz},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/smll.202200605},

doi = {https://doi.org/10.1002/smll.202200605},

issn = {1613-6810},

year  = {2022},

date = {2022-07-29},

journal = {Small},

volume = {18},

number = {34},

pages = {2200605},

abstract = {Abstract In organic electronics, local crystalline order is of critical importance for the charge transport. Grain boundaries between molecularly ordered domains are generally known to hamper or completely suppress charge transfer and detailed knowledge of the local electronic nature is critical for future minimization of such malicious defects. However, grain boundaries are typically hidden within the bulk film and consequently escape observation or investigation. Here, a minimal model system in form of monolayer-thin films with sub-nm roughness of a prototypical n-type organic semiconductor is presented. Since these films consist of large crystalline areas, the detailed energy landscape at single grain boundaries can be studied using Kelvin probe force microscopy. By controlling the charge-carrier density in the films electrostatically, the impact of the grain boundaries on charge transport in organic devices is modeled. First, two distinct types of grain boundaries are identified, namely energetic barriers and valleys, which can coexist within the same thin film. Their absolute height is found to be especially pronounced at charge-carrier densities below 1012 cm\textendash2\textemdashthe regime at which organic solar cells and light emitting diodes typically operate. Finally, processing conditions by which the type or energetic height of grain boundaries can be controlled are identified.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Maximizing the Accessibility in DNA Origami Nanoantenna Plasmonic Hotspots},

author = {C Close and K Trofymchuk and L Grabenhorst and B Lalkens and V Glembockyte and P Tinnefeld},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/admi.202200255},

doi = {https://doi.org/10.1002/admi.202200255},

issn = {2196-7350},

year  = {2022},

date = {2022-07-01},

journal = {Advanced Materials Interfaces},

volume = {n/a},

number = {n/a},

pages = {2200255},

abstract = {Abstract DNA nanotechnology has conquered the challenge of positioning quantum emitters in the hotspot of optical antenna structures for fluorescence enhancement. Therefore, DNA origami serves as the scaffold to arrange nanoparticles and emitters, such as fluorescent dyes. For the next challenge of optimizing the applicability of plasmonic hotspots for molecular assays, a Trident DNA origami structure that increases the accessibility of the hotspot is introduced, thereby improving the kinetics of target molecule binding. This Trident NanoAntenna with Cleared HOtSpot (NACHOS) is compared with previous DNA origami nanoantennas and improved hotspot accessibility is demonstrated without compromising fluorescence enhancement. The approach taps into the potential of Trident NACHOS for single-molecule-based plasmonic biosensing.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Light-driven molecular motors embedded in covalent organic frameworks},

author = {C St\"{a}hler and L Grunenberg and M W Terban and W R Browne and D Doellerer and M Kathan and M Etter and B V Lotsch and B L Feringa and S Krause},

url = {http://dx.doi.org/10.1039/D2SC02282F},

doi = {10.1039/D2SC02282F},

issn = {2041-6520},

year  = {2022},

date = {2022-06-02},

journal = {Chemical Science},

abstract = {The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host\textendashguest phenomena in well-defined 3D solid materials. In this work, we detail the synthesis of a diamine-based light-driven molecular motor and its incorporation into a series of imine-based polymers and covalent organic frameworks (COF). We study structural and dynamic properties of the molecular building blocks and derived self-assembled solids with a series of spectroscopic, diffraction, and theoretical methods. Using an acid-catalyzed synthesis approach, we are able to obtain the first crystalline 2D COF with stacked hexagonal layers that contains 20 mol% molecular motors. The COF features a specific pore volume and surface area of up to 0.45 cm3 g−1 and 604 m2 g−1, respectively. Given the molecular structure and bulkiness of the diamine motor, we study the supramolecular assembly of the COF layers and detail stacking disorders between adjacent layers. We finally probe the motor dynamics with in situ spectroscopic techniques revealing current limitations in the analysis of these new materials and derive important analysis and design criteria as well as synthetic access to new generations of motorized porous framework materials.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Selective and Cooperative Photocycloadditions within Multistranded Aromatic Sheets},

author = {B Gole and B Kauffmann and A Tron and V Maurizot and N Mcclenaghan and I Huc and Y Ferrand},

url = {https://doi.org/10.1021/jacs.2c01269},

doi = {10.1021/jacs.2c01269},

issn = {0002-7863},

year  = {2022},

date = {2022-04-05},

urldate = {2022-04-05},

journal = {Journal of the American Chemical Society},

abstract = {A series of aromatic helix-sheet-helix oligoamide foldamers composed of several different photosensitive diazaanthracene units have been designed and synthesized. Molecular objects up to 7 kDa were straightforwardly produced on a 100 mg scale. Nuclear magnetic resonance and crystallographic investigations revealed that helix-sheet-helix architectures can adopt one or two distinct conformations. Sequences composed of an even number of turn units were found to fold in a canonical symmetrical conformation with two helices of identical handedness stacked above and below the sheet segment. Sequences composed of an odd number of turns revealed a coexistence between a canonical fold with helices of opposite handedness and an alternate fold with a twist within the sheet and two helices of identical handedness. The proportions between these species could be manipulated, in some cases quantitatively, being dependent on solvent, temperature, and absolute control of helix handedness. Diazaanthracene units were shown to display distinct reactivity toward [4 + 4] photocycloadditions according to the substituent in position 9. Their organization within the sequences was programmed to allow photoreactions to take place in a specific order. Reaction pathways and kinetics were deciphered and product characterized, demonstrating the possibility to orchestrate successive photoreactions so as to avoid orphan units or to deliberately produce orphan units at precise locations. Strong cooperative effects were observed in which the photoreaction rate was influenced by the presence (or absence) of photoadducts in the structure. Multiple photoreactions within the aromatic sheet eventually lead to structure lengthening and stiffening, locking conformational equilibria. Photoproducts could be thermally reverted.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Process-aid solid engineering triggers delicately modulation of Y-series non-fullerene acceptor for efficient organic solar cells},

author = {X Song and K Zhang and R Guo and K Sun and Z Zhou and S Huang and L Huber and M Reus and J Zhou and M Schwartzkopf and S V Roth and W Liu and Y Liu and W Zhu and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202200907},

doi = {https://doi.org/10.1002/adma.202200907},

issn = {0935-9648},

year  = {2022},

date = {2022-03-22},

journal = {Advanced Materials},

volume = {n/a},

number = {n/a},

pages = {2200907},

abstract = {Abstract Volatile solids with symmetric π-backbone have been intensively implemented on manipulating the nanomorphology for improving the operability and stability of organic solar cells. However, due to the isotropic stacking, the announced solids with symmetric geometry cannot modify the microscopic phase separation and component distribution collaboratively, which would constrain the promotion of exciton splitting and charge collection efficiency. Inspired by the superiorities of asymmetric configuration, a novel process-aid solid (PAS) engineering is proposed. By coupling with BTP core unit in Y-series molecule, an asymmetric, volatile 1, 3-dibromo-5-chlorobenzene (DBCl) solid can induce the anisotropic dipole direction, elevated dipole moment, and interlaminar interaction spontaneously. Due to the synergetic effects on the favorable phase separation and desired component distribution, the PAS treated devices feature the evident improvement of exciton splitting, charge transport, and collection, accompanied by the suppressed trap-assisted recombination. Consequently, we achieve an impressive fill factor of 80.2% with maximum power conversion efficiency (PCE) of 18.5% in the PAS treated device. More strikingly, the PAS treated devices demonstrate a promising thickness-tolerance character, where a record PCE of 17.0% is yielded in PAS devices with a 300 nm thickness photoactive layer, which represents the highest PCE for thick-film OSCs. This article is protected by copyright. All rights reserved},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Revealing Donor\textendashAcceptor Interaction on the Printed Active Layer Morphology and the Formation Kinetics for Nonfullerene Organic Solar Cells at Ambient Conditions},

author = {X Jiang and P Chotard and K Luo and F Eckmann and S Tu and M A Reus and S Yin and J Reitenbach and C L Weindl and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202103977},

doi = {https://doi.org/10.1002/aenm.202103977},

issn = {1614-6832},

year  = {2022},

date = {2022-02-27},

journal = {Advanced Energy Materials},

volume = {n/a},

number = {n/a},

pages = {2103977},

abstract = {Abstract Slot-die coating is a powerful method for upscaling the production of organic solar cells (OSCs) with low energy consumption print processes at ambient conditions. Herein, chlorobenzene (CB) and chloroform (CF) are compared as host solvents for printing films of the neat novel fused-ring unit based wide-bandgap donor polymer (PDTBT2T-FTBDT), the small molecule nonfullerene acceptor based on a fused ring with a benzothiadiazole core (BTP-4F) as well as the respective PDTBT2T-FTBDT:BTP-4F blend films at room temperature in air. Using CF printing of the PDTBT2T-FTBDT:BTP-4F active layer, OSCs with a high power conversion efficiency of up to 13.2% are reached in ambient conditions. In comparison to CB printed blend films, the active layer printed out of CF has a superior morphology, a smoother film surface and a more pronounced face-on orientation of the crystallites, which altogether result in an enhanced exciton dissociation, a superior charge transport, and suppressed nonradiative charge carrier recombination. Based on in situ studies of the slot-die coating process of PDTBT2T-FTBDT, BTP-4F, and PDTBT2T-FTBDT:BTP-4F films, the details of the film formation kinetics are clarified, which cause the superior behavior for CF compared to CB printing due to balancing the aggregation and crystallization of donor and acceptor.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Direct and Linker-Exchange Alcohol-Assisted Hydrothermal Synthesis of Imide-Linked Covalent Organic Frameworks},

author = {J Maschita and T Banerjee and B V Lotsch},

url = {https://doi.org/10.1021/acs.chemmater.1c04051},

doi = {10.1021/acs.chemmater.1c04051},

issn = {0897-4756},

year  = {2022},

date = {2022-02-17},

journal = {Chemistry of Materials},

abstract = {Covalent organic frameworks (COFs) are an extensively studied class of porous materials, which distinguish themselves from other porous polymers in their crystallinity and high degree of modularity, enabling a wide range of applications. However, the established synthetic protocols for the synthesis of stable and crystalline COFs, such as imide-linked COFs, often requires the use of high boiling solvents and toxic catalysts, making their synthesis expensive and environmentally harmful. Herein, we report a new environmentally friendly strategy─an alcohol-assisted hydrothermal polymerization approach (aaHTP) for the synthesis of a wide range of crystalline and porous imide-linked COFs. This method allows us to gain access to new COFs and to avoid toxic solvents by up to 90% through substituting commonly used organic solvent mixtures with water and small amounts of n-alcohols without being restricted to water-soluble linker molecules. Additionally, we use the aaHTP to demonstrate an eco-friendly COF-to-COF transformation of an imine-linked COF into a novel imide-linked COF via linkage replacement, inaccessible using published reaction conditions.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Solvent Tuning of the Active Layer Morphology of Non-Fullerene Based Organic Solar Cells},

author = {S Grott and A Kotobi and L K Reb and C L Weindl and R Guo and S Yin and K S Wienhold and W Chen and T Ameri and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/solr.202101084},

doi = {https://doi.org/10.1002/solr.202101084},

issn = {2367-198X},

year  = {2022},

date = {2022-02-12},

journal = {Solar RRL},

volume = {n/a},

number = {n/a},

pages = {2101084},

abstract = {Non-fullerene acceptor (NFA)-based organic solar cells have made tremendous progress in recent years. For the neat NFA system PBDB-T:ITIC, the film morphology and crystallinity are tailored by the choice of the solvent used for spin coating the active layers. Three different chlorinated solvents, chlorobenzene (CB), chloroform, and dichlorobenzene, are compared and the obtained active layer morphology is correlated with the optoelectronic properties and the device performance. The small domain sizes in the case of CB are most beneficial for the device performance, whereas the largest number or size of face-on PBDB-T crystallites is not causing the highest power conversion efficiencies (PCEs). In addition, when using CB, the number of edge-on crystallites is highest and the distances between neighboring domains are small. The smoothest blend films are realized with CB, which exhibit correlated roughness with their substrates and no large aggregates have formed in these blend films. Thus, CB offers the best way to balance the aggregation and crystallization kinetics in the active layer and enables the highest PCE values.},

keywords = {Foundry Organic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {All About the Interface: Do Residual Contaminants at A High-Quality h-BN Monolayer Perylene Diimide Interface Cause Charge Trapping?},

author = {L Renn and L S Walter and K Watanabe and T Taniguchi and R T Weitz},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/admi.202101701},

doi = {https://doi.org/10.1002/admi.202101701},

issn = {2196-7350},

year  = {2022},

date = {2022-01-29},

journal = {Advanced Materials Interfaces},

volume = {n/a},

number = {n/a},

pages = {2101701},

abstract = {Abstract Intrinsic charge transport in molecularly thin organic semiconducting crystals is critically sensitive to the quality of the interfaces required to perform the electrical measurements. Most prominent are the dielectric\textendashsemiconductor and semiconductor\textendashmetal interface. While impacts from the latter on charge transport can be extracted by four-terminal measurements, the impact of the dielectric interface can only be minimized, typically by utilizing inert dielectrics. Here, it is shown that charge transport in organic field-effect transistors based on the n-type small molecule N, N′-di((S)-1-methylpentyl)-1,7(6)-dicyano-perylene-3,4:9,10-bis(dicarboximide) (PDI1MPCN2) can be improved up to one order of magnitude by using hexagonal boron nitride (h-BN) as dielectric, compared to a standard SiO2 substrate. Using temperature-dependent electrical measurements, the charge-transport properties of devices are systematically analyzed, and high four-terminal mobilities of up to 5.0 cm2 V−1 s−1 are obtained. The high mobility likely stems from decreased charge-carrier trapping at the semiconductor-dielectric interface due to the smooth surface of the inert h-BN. Nevertheless, the temperature dependencies of the mobility, threshold voltage, and interface-state trap density suggest that charge-carrier trapping at the dielectric-semiconductor interface still exists. By comparing the data to transport studies performed on thin air-gapped organic films, it is concluded that an interfacial layer (likely water or solvent residues) between h-BN and the monolayer PDI1MPCN2 causes charge trapping.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Quantitative Single-Molecule Measurements of Membrane Charges with DNA Origami Sensors},

author = {S E Ochmann and T Schr\"{o}der and C M Schulz and P Tinnefeld},

url = {https://doi.org/10.1021/acs.analchem.1c05092},

doi = {10.1021/acs.analchem.1c05092},

issn = {0003-2700},

year  = {2022},

date = {2022-01-28},

journal = {Analytical Chemistry},

abstract = {Charges in lipid head groups generate electrical surface potentials at cell membranes, and changes in their composition are involved in various signaling pathways, such as T-cell activation or apoptosis. Here, we present a DNA origami-based sensor for membrane surface charges with a quantitative fluorescence read-out of single molecules. A DNA origami plate is equipped with modifications for specific membrane targeting, surface immobilization, and an anionic sensing unit consisting of single-stranded DNA and the dye ATTO542. This unit is anchored to a lipid membrane by the dye ATTO647N, and conformational changes of the sensing unit in response to surface charges are read out by fluorescence resonance energy transfer between the two dyes. We test the performance of our sensor with single-molecule fluorescence microscopy by exposing it to differently charged large unilamellar vesicles. We achieve a change in energy transfer of ∼10% points between uncharged and highly charged membranes and demonstrate a quantitative relation between the surface charge and the energy transfer. Further, with autocorrelation analyses of confocal data, we unravel the working principle of our sensor that is switching dynamically between a membrane-bound state and an unbound state on the timescale of 1\textendash10 ms. Our study introduces a complementary sensing system for membrane surface charges to previously published genetically encoded sensors. Additionally, the single-molecule read-out enables investigations of lipid membranes on the nanoscale with a high spatial resolution circumventing ensemble averaging.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nanoscopic Electrolyte-Gated Vertical Organic Transistors with Low Operation Voltage and Five Orders of Magnitude Switching Range for Neuromorphic Systems},

author = {C Eckel and J Lenz and A Melianas and A Salleo and R T Weitz},

url = {https://doi.org/10.1021/acs.nanolett.1c03832},

doi = {10.1021/acs.nanolett.1c03832},

issn = {1530-6984},

year  = {2022},

date = {2022-01-20},

journal = {Nano Letters},

abstract = {Electrolyte-gated organic transistors (EGOTs) are promising candidates as a new class of neuromorphic devices in hardware-based artificial neural networks that can outperform their complementary metal oxide semiconductor (CMOS) counterparts regarding processing speed and energy consumption. Several ways in which to implement such networks exist, two prominent methods of which can be implemented by nanoscopic vertical EGOTs, as we show here. First, nanoscopic vertical electrolyte-gated transistors with a donor\textendashacceptor diketopyrrolopyrrole\textendashterthiophene polymer as an active material can be used to reversibly switch the channel conductivity over five orders of magnitude (3.8 nS to 392 μS) and perform switching at low operation voltages down to −1 mV. Second, nanoscopic EGOTs can also mimic fundamental synaptic functions, and we show an interconnection of up to three transistors, highlighting the possibility to emulate biological nerve cells.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ultrafast carrier dynamics at organic donor\textendashacceptor interfaces\textemdasha quantum-based assessment of the hopping model},

author = {M F X Dorfner and S Hutsch and R Borrelli and M F Gelin and F Ortmann},

url = {http://dx.doi.org/10.1088/2515-7639/ac442b},

doi = {10.1088/2515-7639/ac442b},

issn = {2515-7639},

year  = {2022},

date = {2022-01-10},

journal = {Journal of Physics: Materials},

volume = {5},

number = {2},

pages = {024001},

abstract = {We investigate the charge transfer dynamics of photogenerated excitons at the donor\textendashacceptor interface of an organic solar cell blend under the influence of molecular vibrations. This is examined using an effective Hamiltonian, parametrized by density functional theory calculations, to describe the full quantum behaviour of the relevant molecular orbitals, which are electronically coupled with each other and coupled to over 100 vibrations (via Holstein coupling). This electron\textendashphonon system is treated in a numerically quasi-exact fashion using the matrix-product-state (MPS) ansatz. We provide insight into different mechanisms of charge separation and their relation to the electronic driving energy for the separation process. We find ultrafast electron transfer, which for small driving energy is dominated by kinetic processes and at larger driving energies by dissipative phonon emission connected to the prevalent vibration modes. Using this fully quantum mechanical model we perform a benchmark comparison to a recently developed semi-classical hopping approach, which treats the hopping and vibration time scales consistently. We find qualitatively and quantitatively good agreement between the results of the sophisticated MPS based quantum dynamics and the simple and fast time-consistent-hopping approach.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Nickel polyphthalocyanine with electronic localization at the nickel site for enhanced CO2 reduction reaction},

author = {K Chen and M Cao and G Ni and S Chen and H Liao and L Zhu and H Li and J Fu and J Hu and E Cort\'{e}s and M Liu},

url = {https://www.sciencedirect.com/science/article/pii/S0926337322000339},

doi = {https://doi.org/10.1016/j.apcatb.2022.121093},

issn = {0926-3373},

year  = {2022},

date = {2022-01-09},

journal = {Applied Catalysis B: Environmental},

volume = {306},

pages = {121093},

abstract = {Nickel phthalocyanine (NiPc) can be at first glance a compelling catalyst for CO2 reduction reaction (CO2RR) because of its Ni\textendashN4 site. Unfortunately, the pristine NiPc possesses a low catalytic activity resulting from the poor CO2 adsorption and activation capabilities of the electron-deficiency Ni site. Herein, we develop nickel polyphthalocyanine (NiPPc) with extended conjugation to tailor the electronic density at the Ni active site. The enlarged π conjugation of NiPPc evokes the d-electrons localization, increasing the electronic density at the Ni site, which enhances its CO2 adsorption and activation. Consequently, NiPPc supported on carbon nanotubes (NiPPc/CNT) in a flow cell delivers an excellent activity of −300 mA cm−2 for CO2RR with the CO selectivity of 99.8%, which is much higher than that of NiPc dispersed on carbon nanotubes. NiPPc/CNT exhibits an outstanding stability for CO2RR of more than 30 h at a current density of −100 mA cm−2 with an ultrahigh selectivity for CO, exceeding 99.7%. This work showcases a new way of tuning the electronic density of catalytic sites.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {In Situ GISAXS Observation and Large Area Homogeneity Study of Slot-Die Printed PS-b-P4VP and PS-b-P4VP/FeCl3 Thin Films},

author = {S Yin and T Tian and C L Weindl and K S Wienhold and Q Ji and Y Cheng and Y Li and C M Papadakis and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.1c19797},

doi = {10.1021/acsami.1c19797},

issn = {1944-8244},

year  = {2022},

date = {2022-01-04},

urldate = {2022-01-04},

journal = {ACS Applied Materials \& Interfaces},

abstract = {Mesoporous hematite (α-Fe2O3) thin films with high surface-to-volume ratios show great potential as photoelectrodes or electrochemical electrodes in energy conversion and storage. In the present work, with the assistance of an up-scalable slot-die coating technique, locally highly ordered α-Fe2O3 thin films are successfully printed based on the amphiphilic diblock copolymer poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) as a structure-directing agent. Pure PS-b-P4VP films are printed under the same conditions for comparison. The micellization of the diblock copolymer in solution, the film formation process of the printed thin films, the homogeneity of the dry films in the lateral and vertical direction as well as the morphological and compositional information on the calcined hybrid PS-b-P4VP/FeCl3 thin film are investigated. Because of convection during the solvent evaporation process, a similar dimple-type structure of vertically aligned cylindrical PS domains in a P4VP matrix developed for both printed PS-b-P4VP and hybrid PS-b-P4VP/FeCl3 thin films. The coordination effect between the Fe3+ ions and the vinylpyridine groups significantly affects the attachment ability of the P4VP chains to the silicon substrate. Accordingly, distinct feature sizes and homogeneity in the lateral direction, as well as the thicknesses in the perpendicular direction, are demonstrated in the two printed films. By removing the polymer template from the hybrid PS-b-P4VP/FeCl3 film at high temperature, a locally highly ordered mesoporous α-Fe2O3 film is obtained. Thus, a facile and up-scalable printing technique is presented for producing homogeneous mesoporous α-Fe2O3 thin films.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity},

author = {S T Emmerling and F Ziegler and F R Fischer and R Schoch and M Bauer and B Plietker and M R Buchmeiser and B V Lotsch},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202104108},

doi = {https://doi.org/10.1002/chem.202104108},

issn = {0947-6539},

year  = {2021},

date = {2021-12-09},

urldate = {2021-12-09},

journal = {Chemistry \textendash A European Journal},

volume = {n/a},

number = {n/a},

pages = {e202104108},

abstract = {Abstract Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as heterogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in α,ω-diene ring-closing metathesis reactions, leading to increased macrocyclization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous olefin metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O=1.35) of up to 51 % compared to the homogeneous catalyst (MMC:O=0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry},

author = {M Aust and A J Herold and L Niederegger and C Schneider and D C Mayer and M Drees and J Warnan and A P\"{o}thig and R A Fischer},

url = {https://doi.org/10.1021/acs.inorgchem.1c03045},

doi = {10.1021/acs.inorgchem.1c03045},

issn = {0020-1669},

year  = {2021},

date = {2021-12-06},

journal = {Inorganic Chemistry},

volume = {60},

number = {24},

pages = {19242-19252},

abstract = {Benzene-1,3,5-tri(dithiocarboxylate) (BTDTC3\textendash), the sulfur-donor analogue of trimesate (BTC3\textendash, benzene-1,3,5-tricarboxylate), is introduced, and its potential as a multidentate, electronically bridging ligand in coordination chemistry is evaluated. For this, the sodium salt Na3BTDTC has been synthesized, characterized, and compared with the sodium salt of the related ditopic benzene-1,4-di(dithiocarboxylate) (Na2BDDTC). Single-crystal X-ray diffraction of the respective tetrahydrofuran (THF) solvates reveals that such multitopic aromatic dithiocarboxylate linkers can form both discrete metal complexes (Na3BTDTC·9THF) and (two-dimensional) coordination polymers (Na2BDDTC·4THF). Additionally, the versatile coordination behavior of the novel BTDTC3\textendash ligand is demonstrated by successful synthesis and characterization of trinuclear Cu(I) and hexanuclear Mo(II)2 paddlewheel complexes. The electronic structure and molecular orbitals of both dithiocarboxylate ligands as well as their carboxylate counterparts are investigated by density functional theory computational methods. Electrochemical investigations suggest that BTDTC3\textendash enables electronic communication between the coordinated metal ions, rendering it a promising tritopic linker for functional coordination polymers.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Ligand Engineering in Nickel Phthalocyanine to Boost the Electrocatalytic Reduction of CO2},

author = {K Chen and M Cao and Y Lin and J Fu and H Liao and Y Zhou and H Li and X Qiu and J Hu and X Zheng and M Shakouri and Q Xiao and Y Hu and J Li and J Liu and E Cort\'{e}s and M Liu},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202111322},

doi = {https://doi.org/10.1002/adfm.202111322},

issn = {1616-301X},

year  = {2021},

date = {2021-12-01},

urldate = {2021-12-01},

journal = {Advanced Functional Materials},

volume = {n/a},

number = {n/a},

pages = {2111322},

abstract = {Abstract Designing and synthesizing efficient molecular catalysts may unlock the great challenge of controlling the CO2 reduction reaction (CO2RR) with molecular precision. Nickel phthalocyanine (NiPc) appears as a promising candidate for this task due to its adjustable Ni active-site. However, the pristine NiPc suffers from poor activity and stability for CO2RR owing to the poor CO2 adsorption and activation at the bare Ni site. Here, a ligand-tuned strategy is developed to enhance the catalytic performance and unveil the ligand effect of NiPc on CO2RR. Theoretical calculations and experimental results indicate that NiPc with electron-donating substituents (hydroxyl or amino) can induce electronic localization at the Ni site which greatly enhances the CO2 adsorption and activation. Employing the optimal catalyst\textemdashan amino-substituted NiPc\textemdashto convert CO2 into CO in a flow cell can achieve an ultrahigh activity and selectivity of 99.8% at current densities up to −400 mA cm−2. This work offers a novel strategy to regulate the electronic structure of active sites by ligand design and discloses the ligand-directed catalysis of the tailored NiPc for highly efficient CO2RR.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Charge transport in semiconducting polymers at the nanoscale},

author = {J Lenz and R T Weitz},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0068098},

doi = {10.1063/5.0068098},

year  = {2021},

date = {2021-11-17},

urldate = {2021-11-17},

journal = {APL Materials},

volume = {9},

number = {11},

pages = {110902},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A flavin-inspired covalent organic framework for photocatalytic alcohol oxidation},

author = {S Trenker and L Grunenberg and T Banerjee and G Savasci and L M Poller and K I M Muggli and F Haase and C Ochsenfeld and B V Lotsch},

url = {http://dx.doi.org/10.1039/D1SC04143F},

doi = {10.1039/D1SC04143F},

issn = {2041-6520},

year  = {2021},

date = {2021-11-15},

urldate = {2021-11-15},

journal = {Chemical Science},

volume = {12},

number = {45},

pages = {15143-15150},

abstract = {Covalent organic frameworks (COFs) offer a number of key properties that predestine them to be used as heterogeneous photocatalysts, including intrinsic porosity, long-range order, and light absorption. Since COFs can be constructed from a practically unlimited library of organic building blocks, these properties can be precisely tuned by choosing suitable linkers. Herein, we report the construction and use of a novel COF (FEAx-COF) photocatalyst, inspired by natural flavin cofactors. We show that the functionality of the alloxazine chromophore incorporated into the COF backbone is retained and study the effects of this heterogenization approach by comparison with similar molecular photocatalysts. We find that the integration of alloxazine chromophores into the framework significantly extends the absorption spectrum into the visible range, allowing for photocatalytic oxidation of benzylic alcohols to aldehydes even with low-energy visible light. In addition, the activity of the heterogeneous COF photocatalyst is less dependent on the chosen solvent, making it more versatile compared to molecular alloxazines. Finally, the use of oxygen as the terminal oxidant renders FEAx-COF a promising and “green” heterogeneous photocatalyst.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Modular Assembly of Vibrationally and Electronically Coupled Rhenium Bipyridine Carbonyl Complexes on Silicon},

author = {J D Bartl and C Thomas and A Henning and M F Ober and G Savasci and B Yazdanshenas and P S Deimel and E Magnano and F Bondino and P Zeller and L Gregoratti and M Amati and C Paulus and F Allegretti and A Cattani-Scholz and J V Barth and C Ochsenfeld and B Nickel and I D Sharp and M Stutzmann and B Rieger},

url = {https://doi.org/10.1021/jacs.1c09061},

doi = {10.1021/jacs.1c09061},

issn = {0002-7863},

year  = {2021},

date = {2021-11-12},

urldate = {2021-11-12},

journal = {Journal of the American Chemical Society},

volume = {143},

pages = {19505},

abstract = {Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.},

keywords = {Foundry Inorganic, Foundry Organic, Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {How Blinking Affects Photon Correlations in Multichromophoric Nanoparticles},

author = {T Schr\"{o}der and S Bange and J Schedlbauer and F Steiner and J M Lupton and P Tinnefeld and J Vogelsang},

url = {https://doi.org/10.1021/acsnano.1c06649},

doi = {10.1021/acsnano.1c06649},

issn = {1936-0851},

year  = {2021},

date = {2021-11-04},

urldate = {2021-11-04},

journal = {ACS Nano},

abstract = {A single chromophore can only emit a maximum of one single photon per excitation cycle. This limitation results in a phenomenon commonly referred to as photon antibunching (pAB). When multiple chromophores contribute to the fluorescence measured, the degree of pAB has been used as a metric to “count” the number of chromophores. But the fact that chromophores can switch randomly between bright and dark states also impacts pAB and can lead to incorrect chromophore numbers being determined from pAB measurements. By both simulations and experiment, we demonstrate how pAB is affected by independent and collective chromophore blinking, enabling us to formulate universal guidelines for correct interpretation of pAB measurements. We use DNA-origami nanostructures to design multichromophoric model systems that exhibit either independent or collective chromophore blinking. Two approaches are presented that can distinguish experimentally between these two blinking mechanisms. The first one utilizes the different excitation intensity dependence on the blinking mechanisms. The second approach exploits the fact that collective blinking implies energy transfer to a quenching moiety, which is a time-dependent process. In pulsed-excitation experiments, the degree of collective blinking can therefore be altered by time gating the fluorescence photon stream, enabling us to extract the energy-transfer rate to a quencher. The ability to distinguish between different blinking mechanisms is valuable in materials science, such as for multichromophoric nanoparticles like conjugated-polymer chains as well as in biophysics, for example, for quantitative analysis of protein assemblies by counting chromophores.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Abiotic Formation of an Amide Bond via Surface-Supported Direct Carboxyl\textendashAmine Coupling},

author = {B Yang and K Niu and F Haag and N Cao and J Zhang and H Zhang and Q Li and F Allegretti and J Bj\"{o}rk and J V Barth and L Chi},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202113590},

doi = {https://doi.org/10.1002/anie.202113590},

issn = {1433-7851},

year  = {2021},

date = {2021-10-28},

journal = {Angewandte Chemie International Edition},

volume = {61},

number = {5},

pages = {e202113590},

abstract = {Abstract Amide bond formation is one of the most important reactions in biochemistry, notably being of crucial importance for the origin of life. Herein, we combine scanning tunneling microscopy and X-ray photoelectron spectroscopy studies to provide evidence for thermally activated abiotic formation of amide bonds between adsorbed precursors through direct carboxyl\textendashamine coupling under ultrahigh-vacuum conditions by means of on-surface synthesis. Complementary insights from temperature-programmed desorption measurements and density functional theory calculations reveal the competition between cross-coupling amide formation and decarboxylation reactions on the Au(111) surface. Furthermore, we demonstrate the critical influence of the employed metal support: whereas on Au(111) the coupling readily occurs, different reaction scenarios prevail on Ag(111) and Cu(111). The systematic experiments signal that archetypical bio-related molecules can be abiotically synthesized in clean environments without water or oxygen.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Water jet space charge spectroscopy: Route to direct measurement of electron dynamics for organic systems in their natural environment},

author = {M Mittermair and F Martin and M W\"{o}rle and D Blo\ss and A Duensing and R Kienberger and A Hans and H Iglev and A Knie and W Helml},

year  = {2021},

date = {2021-10-19},

journal = {arXiv preprint arXiv:2110.10044},

abstract = {The toolbox for time-resolved direct measurements of electron dynamics covers a variety of methods. Since the experimental effort is increasing rapidly with achievable time resolution, there is an urge for simple and robust measurement techniques. Within this paper prove of concept experiments and numerical simulations are utilized to investigate the applicability of a new setup for the generation of ultrashort electron pulses in the energy range of 300 eV up to 1.6 keV. The experimental approach combines an in-vacuum liquid microjet and a few-cycle femtosecond laser system, while the threshold for electron impact ionization serves as a gate for the effective electron pulse duration. The experiments prove that electrons in the keV regime are accessible and that the electron spectrum can be easily tuned by laser intensity and focal position alignment with respect to the water jet. Numerical simulations show that a sub-picosecond temporal resolution is achievable.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {On the origin of chirality in plasmonic meta-molecules},

author = {K Martens and T Funck and E Y Santiago and A O Govorov and S Burger and T Liedl},

url = {https://arxiv.org/abs/2110.06689},

doi = {arXiv:2110.06689v2},

year  = {2021},

date = {2021-10-13},

journal = {arXiv preprint arXiv:2110.06689},

abstract = {Chirality is a fundamental feature in all domains of nature, ranging from particle physics over electromagnetism to chemistry and biology. Chiral objects lack a mirror plane and inversion symmetry and therefore cannot be spatially aligned with their mirrored counterpart, their enantiomer. Both natural molecules and artificial chiral nanostructures can be characterized by their light-matter interaction, which is reflected in circular dichroism (CD). Using DNA origami, we assemble model meta-molecules from multiple plasmonic nanoparticles, representing meta-atoms accurately positioned in space. This allows us to reconstruct piece by piece the impact of varying macromolecular geometries on their surrounding optical near fields. Next to the emergence of CD signatures in the instance that we architect a third dimension, we design and implement sign flipping signals through addition or removal of single particles in the artificial molecules. Our data and theoretical modelling reveal the hitherto unrecognized phenomenon of chiral plasmonic-dielectric coupling, explaining the intricate electromagnetic interactions within hybrid DNA-based plasmonic nanostructures.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {A Critical Outlook for the Pursuit of Lower Contact Resistance in Organic Transistors},

author = {J W Borchert and R T Weitz and S Ludwigs and H Klauk},

doi = {10.1002/adma.202104075},

issn = {0935-9648},

year  = {2021},

date = {2021-10-07},

journal = {Adv Mater},

pages = {e2104075},

abstract = {To take full advantage of recent and anticipated improvements in the performance of organic semiconductors employed in organic transistors, the high contact resistance arising at the interfaces between the organic semiconductor and the source and drain contacts must be reduced significantly. To date, only a small portion of the accumulated research on organic thin-film transistors (TFTs) has reported channel-width-normalized contact resistances below 100 Ωcm, well above what is regularly demonstrated in transistors based on inorganic semiconductors. A closer look at these cases and the relevant literature strongly suggests that the most significant factor leading to the lowest contact resistances in organic TFTs so far has been the control of the thin-film morphology of the organic semiconductor. By contrast, approaches aimed at increasing the charge-carrier density and/or reducing the intrinsic Schottky barrier height have so far played a relatively minor role in achieving the lowest contact resistances. Herein, the possible explanations for these observations are explored, including the prevalence of Fermi-level pinning and the difficulties in forming optimized interfaces with organic semiconductors. An overview of the research on these topics is provided, and potential device-engineering solutions are discussed based on recent advancements in the theoretical and experimental work on both organic and inorganic semiconductors.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Targetable Conformationally Restricted Cyanines Enable Photon-Count-Limited Applications**},

author = {P Eiring and R Mclaughlin and S S Matikonda and Z Han and L Grabenhorst and D A Helmerich and M Meub and G Beliu and M Luciano and V Bandi and N Zijlstra and Z-D Shi and S G Tarasov and R Swenson and P Tinnefeld and V Glembockyte and T Cordes and M Sauer and M J Schnermann},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202109749},

doi = {https://doi.org/10.1002/anie.202109749},

issn = {1433-7851},

year  = {2021},

date = {2021-10-04},

urldate = {2021-10-04},

journal = {Angewandte Chemie International Edition},

volume = {60},

number = {51},

pages = {26685-26693},

abstract = {Abstract Cyanine dyes are exceptionally useful probes for a range of fluorescence-based applications, but their photon output can be limited by trans-to-cis photoisomerization. We recently demonstrated that appending a ring system to the pentamethine cyanine ring system improves the quantum yield and extends the fluorescence lifetime. Here, we report an optimized synthesis of persulfonated variants that enable efficient labeling of nucleic acids and proteins. We demonstrate that a bifunctional sulfonated tertiary amide significantly improves the optical properties of the resulting bioconjugates. These new conformationally restricted cyanines are compared to the parent cyanine derivatives in a range of contexts. These include their use in the plasmonic hotspot of a DNA-nanoantenna, in single-molecule F\"{o}rster-resonance energy transfer (FRET) applications, far-red fluorescence-lifetime imaging microscopy (FLIM), and single-molecule localization microscopy (SMLM). These efforts define contexts in which eliminating cyanine isomerization provides meaningful benefits to imaging performance.},

keywords = {Foundry Inorganic, Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Interlayer Interactions as Design Tool for Large-Pore COFs},

author = {S T Emmerling and R Schuldt and S Bette and L Yao and R E Dinnebier and J K\"{a}stner and B V Lotsch},

url = {https://doi.org/10.1021/jacs.1c06518},

doi = {10.1021/jacs.1c06518},

issn = {0002-7863},

year  = {2021},

date = {2021-09-08},

urldate = {2021-09-08},

journal = {Journal of the American Chemical Society},

volume = {143},

number = {38},

pages = {15711-15722},

abstract = {Covalent organic frameworks (COFs) with a pore size beyond 5 nm are still rarely seen in this emerging field. Besides obvious complications such as the elaborated synthesis of large linkers with sufficient solubility, more subtle challenges regarding large-pore COF synthesis, including pore occlusion and collapse, prevail. Here we present two isoreticular series of large-pore imine COFs with pore sizes up to 5.8 nm and correlate the interlayer interactions with the structure and thermal behavior of the COFs. By adjusting interlayer interactions through the incorporation of methoxy groups acting as pore-directing “anchors”, different stacking modes can be accessed, resulting in modified stacking polytypes and, hence, effective pore sizes. A strong correlation between stacking energy toward highly ordered, nearly eclipsed structures, higher structural integrity during thermal stress, and a novel, thermally induced phase transition of stacking modes in COFs was found, which sheds light on viable design strategies for increased structural control and stability in large-pore COFs.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Single Antibody Detection in a DNA Origami Nanoantenna},

author = {M Pfeiffer and K Trofymchuk and S Ranallo and F Ricci and F Steiner and F Cole and V Glembockyte and P Tinnefeld},

url = {https://www.sciencedirect.com/science/article/pii/S2589004221010403},

doi = {https://doi.org/10.1016/j.isci.2021.103072},

issn = {2589-0042},

year  = {2021},

date = {2021-09-01},

urldate = {2021-09-01},

journal = {iScience},

pages = {103072},

abstract = {Summary DNA nanotechnology offers new biosensing approaches by templating different sensor and transducer components. Here, we combine DNA origami nanoantennas with label-free antibody detection by incorporating a nanoswitch in the plasmonic hotspot of the nanoantenna. The nanoswitch contains two antigens that are displaced by antibody binding thereby eliciting a fluorescent signal. Single antibody detection is demonstrated with a DNA origami integrated anti-digoxigenin antibody nanoswitch. In combination with the nanoantenna, the signal generated by the antibody is additionally amplified. This allows the detection of single antibodies on a portable smartphone microscope. Overall, fluorescence enhanced antibody detection in DNA origami nanoantennas shows that fluorescence enhanced biosensing can be expanded beyond the scope of the nucleic acids realm.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Selective functionalization of the 1H-imidazo[1,2-b]pyrazole scaffold. A new potential non-classical isostere of indole and a precursor of push\textendashpull dyes},

author = {K Schw\"{a}rzer and S K Rout and D Bessinger and F Lima and C E Brocklehurst and K Karaghiosoff and T Bein and P Knochel},

url = {http://dx.doi.org/10.1039/D1SC04155J},

doi = {10.1039/D1SC04155J},

issn = {2041-6520},

year  = {2021},

date = {2021-08-30},

urldate = {2021-08-30},

journal = {Chemical Science},

volume = {12},

number = {39},

pages = {12993-13000},

abstract = {We report the selective functionalization of the 1H-imidazo[1,2-b]pyrazole scaffold using a Br/Mg-exchange, as well as regioselective magnesiations and zincations with TMP-bases (TMP = 2,2,6,6-tetramethylpiperidyl), followed by trapping reactions with various electrophiles. In addition, we report a fragmentation of the pyrazole ring, giving access to push\textendashpull dyes with a proaromatic (1,3-dihydro-2H-imidazol-2-ylidene)malononitrile core. These functionalization methods were used in the synthesis of an isostere of the indolyl drug pruvanserin. Comparative assays between the original drug and the isostere showed that a substitution of the indole ring with a 1H-imidazo[1,2-b]pyrazole results in a significantly improved solubility in aqueous media.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage},

author = {V Stavila and S Li and C Dun and M T Marple and H E Mason and J L Snider and J E Reynolds Iii and F El Gabaly and J D Sugar and C D Spataru and X Zhou and B Dizdar and E H Majzoub and R Chatterjee and J Yano and H Schlomberg and B V Lotsch and J J Urban and B C Wood and M D Allendorf},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202107507},

doi = {https://doi.org/10.1002/anie.202107507},

issn = {1433-7851},

year  = {2021},

date = {2021-08-29},

journal = {Angewandte Chemie International Edition},

volume = {60},

number = {49},

pages = {25815-25824},

abstract = {Abstract The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH3@CTF-bipyridine). This material and the counterpart AlH3@CTF-biphenyl rapidly desorb H2 between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, 27Al MAS NMR and 27Al1H REDOR experiments, and computational spectroscopy reveal that AlH3@CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, \>10 times lower pressure than that required to hydrogenate bulk aluminum. DFT calculations and EPR measurements support an unconventional mechanism whereby strong AlH3 binding to bipyridine results in single-electron transfer to form AlH2(AlH3)n clusters. The resulting size-dependent charge redistribution alters the dehydrogenation/rehydrogenation thermochemistry, suggesting a novel strategy to enable reversibility in high-capacity metal hydrides.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {DNA Origami Nanoantennas for Fluorescence Enhancement},

author = {V Glembockyte and L Grabenhorst and K Trofymchuk and P Tinnefeld},

url = {https://doi.org/10.1021/acs.accounts.1c00307},

doi = {10.1021/acs.accounts.1c00307},

issn = {0001-4842},

year  = {2021},

date = {2021-08-26},

urldate = {2021-08-26},

journal = {Accounts of Chemical Research},

volume = {54},

number = {17},

pages = {3338-3348},

abstract = {ConspectusThe possibility to increase fluorescence by plasmonic effects in the near-field of metal nanostructures was recognized more than half a century ago. A major challenge, however, was to use this effect because placing single quantum emitters in the nanoscale plasmonic hotspot remained unsolved for a long time. This not only presents a chemical problem but also requires the nanostructure itself to be coaligned with the polarization of the excitation light. Additional difficulties arise from the complex distance dependence of fluorescence emission: in contrast to other surface-enhanced spectroscopies (such as Raman spectroscopy), the emitter should not be placed as close as possible to the metallic nanostructure but rather needs to be at an optimal distance on the order of a few nanometers to avoid undesired quenching effects.Our group addressed these challenges almost a decade ago by exploiting the unique positioning ability of DNA nanotechnology and reported the first self-assembled DNA origami nanoantennas. This Account summarizes our work spanning from this first proof-of-principle study to recent advances in utilizing DNA origami nanoantennas for single DNA molecule detection on a portable smartphone microscope.We summarize different aspects of DNA origami nanoantennas that are essential for achieving strong fluorescence enhancement and discuss how single-molecule fluorescence studies helped us to gain a better understanding of the interplay between fluorophores and plasmonic hotspots. Practical aspects of preparing the DNA origami nanoantennas and extending their utility are also discussed.Fluorescence enhancement in DNA origami nanoantennas is especially exciting for signal amplification in molecular diagnostic assays or in single-molecule biophysics, which could strongly benefit from higher time resolution. Additionally, biophysics can greatly profit from the ultrasmall effective detection volumes provided by DNA nanoantennas that allow single-molecule detection at drastically elevated concentrations as is required, e.g., in single-molecule DNA sequencing approaches.Finally, we describe our most recent progress in developing DNA NanoAntennas with Cleared HOtSpots (NACHOS) that are fully compatible with biomolecular assays. The developed DNA origami nanoantennas have proven robustness and remain functional after months of storage. As an example, we demonstrated for the first time the single-molecule detection of DNA specific to antibiotic-resistant bacteria on a portable and battery-driven smartphone microscope enabled by DNA origami nanoantennas. These recent developments mark a perfect moment to summarize the principles and the synthesis of DNA origami nanoantennas and give an outlook of new exciting directions toward using different nanomaterials for the construction of nanoantennas as well as for their emerging applications.},

keywords = {Foundry Inorganic, Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Full Dynamics Description of Mg Phthalocyanine Crystalline and Amorphous Semiconductor Systems},

author = {D Potamianos and M Nuber and A Schletter and M Schnitzenbaumer and M Haimerl and P Scigalla and M W\"{o}rle and L I Wagner and R Kienberger and H Iglev},

url = {https://doi.org/10.1021/acs.jpcc.1c04698},

doi = {10.1021/acs.jpcc.1c04698},

issn = {1932-7447},

year  = {2021},

date = {2021-08-16},

journal = {The Journal of Physical Chemistry C},

abstract = {Based on visible and mid-infrared transient absorption studies, probing the inter- and intraband dynamics, respectively, of magnesium phthalocyanine (MgPc) organic semiconductors, we were able to develop a model to describe the dynamics and the resulting optical response. We demonstrate how the model could offer insights into the dynamics of more complicated systems such as amorphous MgPc samples obtained by established preparation methods. In particular, we show a clear dimensionality difference of the exciton dissipation mechanism between crystalline and amorphous MgPc, which we resolve in the intraband dynamics, and how this result can also be deduced from the interband dynamics through the implementation of the developed model.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}