Publications

@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 = {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},

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}

}

@article{nokey,

title = {Recent Advances in Cross-Couplings of Functionalized Organozinc Reagents},

author = {B Wei and P Knochel},

url = {https://www.thieme-connect.com/products/ejournals/abstract/10.1055/a-1589-0150},

doi = {10.1055/a-1589-0150},

issn = {0039-7881 DOI - 10.1055/a-1589-0150},

year  = {2021},

date = {2021-08-16},

journal = {Synthesis},

volume = {54},

number = {02},

pages = {246-254},

abstract = {Cross-couplings involving organozinc reagents usually require a Pd-catalyst (Negishi cross-coupling), however, uncatalyzed cross-couplings of zinc organometallics proceed well in the absence of transition-metal catalysts with reactive electrophiles such as benzal 1,1-diacetates, benzhydryl acetates, and iminium trifluoroacetates. Organozinc compounds also undergo C\textendashN bond formation with O-benzoylhydroxylamines or organic azides in the presence of cobalt- or iron-catalysts. Highly diastereoselective and enantioselective cross-couplings can be readily performed with room-temperature configurationally stable alkylzinc species, producing diastereoselectively and enantiomerically enriched products. Finally, highly regioselective magnesiations of functionalized arenes and heteroarenes undergo Negishi (after transmetalation with ZnCl2) or Cu-catalyzed cross-couplings.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Short Excited‐State Lifetimes Mediate Charge‐Recombination Losses in Organic Solar Cell Blends with Low Charge‐Transfer Driving Force},

author = {R Shivhare and G J Moore and A Hofacker and S Hutsch and Y Zhong and M Hambsch and T Erdmann and A Kiriy and S C Mannsfeld and F Ortmann},

issn = {0935-9648},

year  = {2021},

date = {2021-08-15},

journal = {Advanced Materials},

pages = {2101784},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Advanced Printed Semiconductors for Energy and Electronic Applications},

author = {T Ameri and L Ke and N Gasparini and R Soltani and M G\"{u}nther and A Buyruk and A A Amin},

url = {https://www.proceedings.iaamonline.org/image/article/1628028399Tayebeh-Ameri---Abstract.pdf},

doi = {https://www.proceedings.iaamonline.org/image/article/1628028399Tayebeh-Ameri---Abstract.pdf},

year  = {2021},

date = {2021-08-03},

urldate = {2021-08-03},

journal = {Video Proceedings of Advanced Materials},

volume = {2},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Electro-mediated PhotoRedox Catalysis for Selective C(sp3)-O Cleavages of Phosphinated Alcohols to Carbanions},

author = {X Tian and T A Karl and S Reiter and S Yakubov and R De Vivie-Riedle and B Koenig and J P Barham},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202105895},

doi = {https://doi.org/10.1002/anie.202105895},

issn = {1433-7851},

year  = {2021},

date = {2021-06-24},

urldate = {2021-06-24},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp 3 )-O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E -selective and can be made Z -selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for a more intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp 3 )-O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions i) tolerate aryl chlorides/bromides and ii) do not give rise to Birch-type reductions.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {The Influence of the Blend Ratio, Solvent Additive, and Post-production Treatment on the Polymer Dynamics in PTB7:PCBM Blend Films},

author = {D M Schwaiger and W Lohstroh and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acs.macromol.1c00313},

doi = {10.1021/acs.macromol.1c00313},

issn = {0024-9297},

year  = {2021},

date = {2021-06-23},

urldate = {2021-06-23},

journal = {Macromolecules},

abstract = {The polymer dynamics inside a bulk heterojunction (BHJ), as used in organic solar cells, are investigated with quasielastic neutron scattering to study hydrogen motion in the polymer side chains. Different blend ratios of the polymer donor poly(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl) (PTB7) and the small molecule acceptor [6,6]phenyl-C71-butyric acid methyl ester (PCBM) are investigated. In addition, the influence of performance-enhancing measures, such as the use of the solvent additive 1,8-diiodooctane (DIO) and the post-production treatment of the BHJ films with methanol, on the polymer dynamics is studied. The analysis of mean square displacements as well as relaxation times of diffusional motions of the hydrogen atoms, located mainly in the polymer side chains, shows a gradual stiffening of the PTB7 side chains for higher PCBM loading in the BHJ films. The presence of DIO significantly increases diffusive mobility inside the films, while the methanol treatment does not affect hydrogen motions.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Band gap engineering in blended organic semiconductor films based on dielectric interactions},

author = {K Ortstein and S Hutsch and M Hambsch and K Tvingstedt and B Wegner and J Benduhn and J Kublitski and M Schwarze and S Schellhammer and F Talnack and A Vogt and P B\"{a}uerle and N Koch and S C B Mannsfeld and H Kleemann and F Ortmann and K Leo},

url = {https://doi.org/10.1038/s41563-021-01025-z},

doi = {10.1038/s41563-021-01025-z},

issn = {1476-4660},

year  = {2021},

date = {2021-06-10},

urldate = {2021-06-10},

journal = {Nature Materials},

abstract = {Blending organic molecules to tune their energy levels is currently being investigated as an approach to engineer the bulk and interfacial optoelectronic properties of organic semiconductors. It has been proven that the ionization energy and electron affinity can be equally shifted in the same direction by electrostatic effects controlled by blending similar halogenated derivatives with different energetics. Here we show that the energy gap of organic semiconductors can also be tuned by blending. We use oligothiophenes with different numbers of thiophene rings as an example and investigate their structure and electronic properties. Photoelectron spectroscopy and inverse photoelectron spectroscopy show tunability of the single-particle gap, with the optical gaps showing similar, but smaller, effects. Theoretical analysis shows that this tuning is mainly caused by a change in the dielectric constant with blend ratio. Further studies will explore the practical impact of this energy-level engineering strategy for optoelectronic devices.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {In situ monitoring of mechanochemical covalent organic framework formation reveals templating effect of liquid additive},

author = {S T Emmerling and L S Germann and P A Julien and I Moudrakovski and M Etter and T Fri\v{s}\v{c}i\'{c} and R E Dinnebier and B V Lotsch},

url = {https://www.sciencedirect.com/science/article/pii/S2451929421002138},

doi = {https://doi.org/10.1016/j.chempr.2021.04.012},

issn = {2451-9294},

year  = {2021},

date = {2021-06-10},

journal = {Chem},

volume = {7},

number = {6},

pages = {1639-1652},

abstract = {Summary Covalent organic frameworks (COFs) have emerged as a new class of molecularly precise, porous functional materials characterized by broad structural and chemical versatility, with a diverse range of applications. Despite their increasing popularity, fundamental aspects of COF formation are poorly understood, lacking profound experimental insights into their assembly. Here, we use a combination of in situ X-ray powder diffraction and Raman spectroscopy to elucidate the reaction mechanism of mechanochemical synthesis of imine COFs, leading to the observation of key reaction intermediates that offer direct experimental evidence of framework templating through liquid additives. Moreover, the solid-state catalyst scandium triflate is instrumental in directing the reaction kinetics and mechanism, yielding COFs with crystallinity and porosity on par with solvothermal products. This work provides the first experimental evidence of solvent-based COF templating and is a significant advancement in mechanistic understanding of mechanochemistry as a green route for COF synthesis.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Dual Nanoresonators for Ultrasensitive Chiral Detection},

author = {E Mohammadi and A Tittl and K L Tsakmakidis and T V Raziman and A G Curto},

url = {https://doi.org/10.1021/acsphotonics.1c00311},

doi = {10.1021/acsphotonics.1c00311},

year  = {2021},

date = {2021-05-28},

journal = {ACS Photonics},

abstract = {The discrimination of enantiomers is crucial in biochemistry. However, chiral sensing faces significant limitations due to inherently weak chiroptical signals. Nanophotonics is a promising solution to enhance sensitivity thanks to increased optical chirality maximized by strong electric and magnetic fields. Metallic and dielectric nanoparticles can separately provide electric and magnetic resonances. Here we propose their synergistic combination in hybrid metal\textendashdielectric nanostructures to exploit their dual character for superchiral fields beyond the limits of single particles. For optimal optical chirality, in addition to maximization of the resonance strength, the resonances must spectrally coincide. Simultaneously, their electric and magnetic fields must be parallel and π/2 out of phase and spatially overlap. We demonstrate that the interplay between the strength of the resonances and these optimal conditions constrains the attainable optical chirality in resonant systems. Starting from a simple symmetric nanodimer, we derive closed-form expressions elucidating its fundamental limits of optical chirality. Building on the trade-offs of different classes of dimers, we then suggest an asymmetric dual dimer based on realistic materials. These dual nanoresonators provide strong and decoupled electric and magnetic resonances together with optimal conditions for chiral fields. Finally, we introduce more complex dual building blocks for a metasurface with a record 300-fold enhancement of local optical chirality in nanoscale gaps, enabling circular dichroism enhancement by a factor of 20. By combining analytical insight and practical designs, our results put forward hybrid resonators to increase chiral sensitivity, particularly for small molecular quantities.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Loading linear arrays of Cu(II) inside aromatic amide helices},

author = {J Wang and B Wicher and A M\'{e}ndez-Ardoy and X Li and G Pecastaings and T Buffeteau and D M Bassani and V Maurizot and I Huc},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202104734},

doi = {https://doi.org/10.1002/anie.202104734},

issn = {1433-7851},

year  = {2021},

date = {2021-05-20},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {The very stable helices of 8-amino-2-quinolinecarboxylic acid oligoamides are shown to uptake Cu(II) ions in their cavity through deprotonation of their amide functions with minimal alteration of their shape, unlike most metallo-organic structures which generally much differ from their organic precursors. The outcome is the formation of intramolecular linear arrays of a defined number of Cu(II) centers (up to sixteen in this study) at a 3 r{A} distance, forming a molecular mimic of a metal wire completely surrounded by an organic sheath. The helices pack in the solid state so that the arrays of Cu(II) extend intermolecularly. Conductive-AFM and cyclic voltammetry suggest that electrons are transported throughout the metal-loaded helices in contrast with hole transport observed for analogous foldamers devoid of metal ions.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Electronic and Geometric Characterization of TICT Formation in Hemithioindigo Photoswitches by Picosecond Infrared Spectroscopy},

author = {K Stallhofer and M Nuber and F Sch\"{u}ppel and S Thumser and H Iglev and R De Vivie-Riedle and W Zinth and H Dube},

url = {https://doi.org/10.1021/acs.jpca.1c02646},

doi = {10.1021/acs.jpca.1c02646},

issn = {1089-5639},

year  = {2021},

date = {2021-05-14},

urldate = {2021-05-14},

journal = {The Journal of Physical Chemistry A},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Coherent vibrational dynamics reveals lattice anharmonicity in organic\textendashinorganic halide perovskite nanocrystals},

author = {T Debnath and D Sarker and H Huang and Z-K Han and A Dey and L Polavarapu and S V Levchenko and J Feldmann},

url = {https://doi.org/10.1038/s41467-021-22934-2},

doi = {10.1038/s41467-021-22934-2},

issn = {2041-1723},

year  = {2021},

date = {2021-05-11},

journal = {Nature Communications},

volume = {12},

number = {1},

pages = {2629},

abstract = {The halide ions of organic-inorganic hybrid perovskites can strongly influence the interaction between the central organic moiety and the inorganic metal halide octahedral units and thus their lattice vibrations. Here, we report the halide-ion-dependent vibrational coherences in formamidinium lead halide (FAPbX3, X = Br, I) perovskite nanocrystals (PNCs) via the combination of femtosecond pump\textendashprobe spectroscopy and density functional theory calculations. We find that the FAPbX3 PNCs generate halide-dependent coherent vibronic wave packets upon above-bandgap non-resonant excitation. More importantly, we observe several higher harmonics of the fundamental modes for FAPbI3 PNCs as compared to FAPbBr3 PNCs. This is likely due to the weaker interaction between the central FA moiety and the inorganic cage for FAPbI3 PNCs, and thus the PbI64− unit can vibrate more freely. This weakening reveals the intrinsic anharmonicity in the Pb-I framework, and thus facilitating the energy transfer into overtone and combination bands. These findings not only unveil the superior stability of Br\textendashbased PNCs over I\textendashbased PNCs but are also important for a better understanding of their electronic and polaronic properties.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Dehydrogenative 6π heterocyclization under visible light irradiation and mechanistic insights},

author = {Z Zhang and H Chen and N Keller and Q Xiong and L Liu and Y Lan and T Bein and J Li},

url = {http://dx.doi.org/10.1039/D1QO00356A},

doi = {10.1039/D1QO00356A},

year  = {2021},

date = {2021-05-07},

journal = {Organic Chemistry Frontiers},

volume = {8},

number = {14},

pages = {3788-3795},

abstract = {A visible-light-driven oxidative 6π heterocyclization for the synthesis of structurally diverse π-conjugated polycyclic 1-aminoisoquinolines has been developed. The reaction proceeds under visible-light or sunlight, obviates the need for photocatalysts and transition-metals, and features an unusually broad substrate scope and high efficacy. This synthetic pathway provided an easy access to highly fluorescent small molecules with high photoluminescence quantum yields. The N-heterocycles exhibit suitable optical properties for application as fluorescence quantum yield standards. DFT calculations were employed to gain insight into the mechanism and the results show that deprotonation is the rate-determining step, which can be promoted by a TFA additive.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {High-Performance Vertical Organic Transistors of Sub-5 nm Channel Length},

author = {J Lenz and A M Seiler and F R Geisenhof and F Winterer and K Watanabe and T Taniguchi and R T Weitz},

url = {https://doi.org/10.1021/acs.nanolett.1c01144},

doi = {10.1021/acs.nanolett.1c01144},

issn = {1530-6984},

year  = {2021},

date = {2021-05-06},

journal = {Nano Letters},

abstract = {Miniaturization of electronic circuits increases their overall performance. So far, electronics based on organic semiconductors has not played an important role in the miniaturization race. Here, we show the fabrication of liquid electrolyte gated vertical organic field effect transistors with channel lengths down to 2.4 nm. These ultrashort channel lengths are enabled by using insulating hexagonal boron nitride with atomically precise thickness and flatness as a spacer separating the vertically aligned source and drain electrodes. The transistors reveal promising electrical characteristics with output current densities of up to 2.95 MA cm\textendash2 at −0.4 V bias, on\textendashoff ratios of up to 106, a steep subthreshold swing of down to 65 mV dec\textendash1 and a transconductance of up to 714 S m\textendash1. Realizing channel lengths in the sub-5 nm regime and operation voltages down to 100 μV proves the potential of organic semiconductors for future highly integrated or low power electronics.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Graphene Energy Transfer for Single-Molecule Biophysics, Biosensing, and Super-Resolution Microscopy},

author = {I Kami\'{n}ska and J Bohlen and R Yaadav and P Sch\"{u}ler and M Raab and T Schr\"{o}der and J Z\"{a}hringer and K Zielonka and S Krause and P Tinnefeld},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202101099},

doi = {https://doi.org/10.1002/adma.202101099},

issn = {0935-9648},

year  = {2021},

date = {2021-05-03},

urldate = {2021-05-03},

journal = {Advanced Materials},

volume = {n/a},

number = {n/a},

pages = {2101099},

abstract = {Abstract Graphene is considered a game-changing material, especially for its mechanical and electrical properties. This work exploits that graphene is almost transparent but quenches fluorescence in a range up to ≈40 nm. Graphene as a broadband and unbleachable energy-transfer acceptor without labeling, is used to precisely determine the height of molecules with respect to graphene, to visualize the dynamics of DNA nanostructures, and to determine the orientation of F\"{o}rster-type resonance energy transfer (FRET) pairs. Using DNA origami nanopositioners, biosensing, single-molecule tracking, and DNA PAINT super-resolution with <3 nm z-resolution are demonstrated. The range of examples shows the potential of graphene-on-glass coverslips as a versatile platform for single-molecule biophysics, biosensing, and super-resolution microscopy.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Photovoltaic Cells Based on Ternary P3HT:PCBM:Ruthenium(II) Complex Bearing 8-(diphenylphosphino)quinoline Active Layer},

author = {S Akel and M A Sharif and R Al-Esseili and M A Al-Wahish and H A Hodali and P M\"{u}ller-Buschbaum and L Schmidt-Mende and M Al-Hussein},

url = {https://www.sciencedirect.com/science/article/pii/S0927775721005549},

doi = {https://doi.org/10.1016/j.colsurfa.2021.126685},

issn = {0927-7757},

year  = {2021},

date = {2021-04-24},

urldate = {2021-04-24},

journal = {Colloids and Surfaces A: Physicochemical and Engineering Aspects},

pages = {126685},

abstract = {ABSTRACT Optical, morphological and photovoltaic properties are investigated for ternary solar cells containing a traditional poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C61-butyric-acid-methyl ester (P3HT:PCBM) bulkheterojunction (BHJ) active layer modified with different concentrations of a novel ruthenium complex [Ru(N-P)2(O-O)], where N-P abbreviates 8-(diphenylphosphino)quinolone and O-O = oxalate dianion. At a low concentration of the Ru-complex (2.5wt. %) the device efficiency is improved by 50% compared with the reference binary devices at ambient conditions. This substantial efficiency enhancement is attributed to the role of the Ru-complex in improving light absorption over a wavelength range of (295-800nm) in combination with a better matching of the energy levels of the ternary blend system. Moreover, at low concentration, the Ru-complex has a positive impact on the morphology of the active layer in the device. The inclusion of Ru-complex increases the P3HT crystallinity substantially with virtually no effect on the size and orientation of the crystalline lamellae. The enhancement in device efficiency becomes less pronounced with increasing the concentration of the Ru-complex due to the formation of several micron-size domains of [Ru(N-P)2(O-O)] in the ternary active layers. These large domains negatively affect the optical properties and morphology, thus inhibiting efficient charge generation and transport in the corresponding solar cells.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Increasing Photostability of Inverted Nonfullerene Organic Solar Cells by Using Fullerene Derivative Additives},

author = {M G\"{u}nther and D Bl\"{a}tte and A L Oechsle and S S Rivas and Yousefi A A Amin and P M\"{u}ller-Buschbaum and T Bein and T Ameri},

url = {https://doi.org/10.1021/acsami.1c00700},

doi = {10.1021/acsami.1c00700},

issn = {1944-8244},

year  = {2021},

date = {2021-04-16},

urldate = {2021-04-16},

journal = {ACS Applied Materials \& Interfaces},

abstract = {Organic solar cells (OSCs) recently achieved efficiencies of over 18% and are well on their way to practical applications, but still considerable stability issues need to be overcome. One major problem emerges from the electron transport material zinc oxide (ZnO), which is mainly used in the inverted device architecture and decomposes many high-performance nonfullerene acceptors due to its photocatalytic activity. In this work, we add three different fullerene derivatives\textemdashPC71BM, ICMA, and BisPCBM\textemdashto an inverted binary PBDB-TF:IT-4F system in order to suppress the photocatalytic degradation of IT-4F on ZnO via the radical scavenging abilities of the fullerenes. We demonstrate that the addition of 5% fullerene not only increases the performance of the binary PBDB-TF:IT-4F system but also significantly improves the device lifetime under UV illumination in an inert atmosphere. While the binary devices lose 20% of their initial efficiency after only 3 h, this time is increased fivefold for the most promising ternary devices with ICMA. We attribute this improvement to a reduced photocatalytic decomposition of IT-4F in the ternary system, which results in a decreased recombination. We propose that the added fullerenes protect the IT-4F by acting as a sacrificial reagent, thereby suppressing the trap state formation. Furthermore, we show that the protective effect of the most promising fullerene ICMA is transferable to two other binary systems PBDB-TF:BTP-4F and PTB7-Th:IT-4F. Importantly, this effect can also increase the air stability of PBDB-TF:IT-4F. This work demonstrates that the addition of fullerene derivatives is a transferable and straightforward strategy to improve the stability of OSCs.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Graphene-on-Glass Preparation and Cleaning Methods Characterized by Single-Molecule DNA Origami Fluorescent Probes and Raman Spectroscopy},

author = {S Krause and E Ploetz and J Bohlen and P Sch\"{u}ler and R Yaadav and F Selbach and F Steiner and I Kami\'{n}ska and P Tinnefeld},

url = {https://pubs.acs.org/doi/abs/10.1021/acsnano.0c08383},

doi = {10.1021/acsnano.0c08383},

issn = {1936-0851},

year  = {2021},

date = {2021-04-09},

urldate = {2021-04-09},

journal = {ACS Nano},

abstract = {Graphene exhibits outstanding fluorescence quenching properties that can become useful for biophysics and biosensing applications, but it remains challenging to harness these advantages due to the complex transfer procedure of chemical vapor deposition-grown graphene to glass coverslips and the low yield of usable samples. Here, we screen 10 graphene-on-glass preparation methods and present an optimized protocol. To obtain the required quality for single-molecule and super-resolution imaging on graphene, we introduce a graphene screening method that avoids consuming the investigated sample. We apply DNA origami nanostructures to place fluorescent probes at a defined distance on top of graphene-on-glass coverslips. Subsequent fluorescence lifetime imaging directly reports on the graphene quality, as deviations from the expected fluorescence lifetime indicate imperfections. We compare the DNA origami probes with conventional techniques for graphene characterization, including light microscopy, atomic force microscopy, and Raman spectroscopy. For the latter, we observe a discrepancy between the graphene quality implied by Raman spectra in comparison to the quality probed by fluorescence lifetime quenching measured at the same position. We attribute this discrepancy to the difference in the effective area that is probed by Raman spectroscopy and fluorescence quenching. Moreover, we demonstrate the applicability of already screened and positively evaluated graphene for studying single-molecule conformational dynamics on a second DNA origami structure. Our results constitute the basis for graphene-based biophysics and super-resolution microscopy.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Long- and short-ranged chiral interactions in DNA-assembled plasmonic chains},

author = {K Martens and F Binkowski and L Nguyen and L Hu and A O Govorov and S Burger and T Liedl},

url = {https://doi.org/10.1038/s41467-021-22289-8},

doi = {10.1038/s41467-021-22289-8},

issn = {2041-1723},

year  = {2021},

date = {2021-04-01},

journal = {Nature Communications},

volume = {12},

number = {1},

pages = {2025},

abstract = {Circular dichroism (CD) has long been used to trace chiral molecular states and changes of protein configurations. In recent years, chiral plasmonic nanostructures have shown potential for applications ranging from pathogen sensing to novel optical materials. The plasmonic coupling of the individual elements of such metallic structures is a crucial prerequisite to obtain sizeable CD signals. We here identify and implement various coupling entities\textemdashchiral and achiral\textemdashto demonstrate chiral transfer over distances close to 100 nm. The coupling is realized by an achiral nanosphere situated between a pair of gold nanorods that are arranged far apart but in a chiral fashion using DNA origami. The transmitter particle causes a strong enhancement of the CD response, the emergence of an additional chiral feature at the resonance frequency of the nanosphere, and a redshift of the longitudinal plasmonic resonance frequency of the nanorods. Matching numerical simulations elucidate the intricate chiral optical fields in complex architectures.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Biocompatible carbon nitride-based light-driven microswimmer propulsion in biological and ionic media with responsive on-demand drug delivery},

author = {V Sridhar and F Podjaski and Y Alapan and J Kr\"{o}ger and L Grunenberg and V Kishore and B V Lotsch and M Sitti},

url = {https://arxiv.org/abs/2103.17026},

doi = {arXiv:2103.17026v1},

year  = {2021},

date = {2021-03-31},

journal = {arXiv preprint arXiv:2103.17026},

abstract = {We propose two-dimensional organic poly(heptazine imide) (PHI) carbon nitride microparticles as light-driven microswimmers in various ionic and biological media. Their demonstrated high-speed (15-23 μm/s) swimming in multi-component ionic solutions with concentrations up to 1 M and without dedicated fuels is unprecedented, overcoming one of the bottlenecks of previous light-driven microswimmers. Such high ion tolerance is attributed to a favorable interplay between the particle's textural and structural nanoporosity and optoionic properties, facilitating ionic interactions in solutions with high salinity. Biocompatibility of the microswimmers is validated by cell viability tests with three different cell types and primary cells. The nanopores of the swimmers are loaded with a model cancer drug, doxorubicin (DOX), in high (185%) loading efficiency without passive release. Controlled drug release is reported in different pH conditions and can be triggered on-demand also by illumination. Light-triggered, boosted release of DOX and its active degradation products is demonstrated in oxygen-poor conditions using the intrinsic, environmentally sensitive and light-induced charge storage properties of PHI, which could enable future theranostic applications in oxygen-deprived tumor regions. These organic PHI microswimmers simultaneously solve the current light-driven microswimmer challenges of high ion tolerance, fuel-free high-speed propulsion in biological media, biocompatibility and controlled on-demand cargo release towards their biomedical, environmental and other potential future applications.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}