TY - JOUR A1 - Hecht, Markus A1 - Leowanawat, Pawaret A1 - Gerlach, Tabea A1 - Stepanenko, Vladimir A1 - Stolte, Matthias A1 - Lehmann, Matthias A1 - Würthner, Frank T1 - Self‐Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra‐Bay‐Acyloxy Perylene Bisimide JF - Angewandte Chemie International Edition N2 - A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self‐assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen‐bond‐directed self‐assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid‐crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo‐ or heterochiral self‐assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self‐sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self‐assemblies proceeds by dissociation via the monomeric state. KW - liquid crystals KW - noncovalent interactions KW - self-assembly KW - structure elucidation KW - supramolecular chemistry Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-224586 VL - 59 IS - 39 SP - 17084 EP - 17090 ER - TY - JOUR A1 - Hoche, Joscha A1 - Schulz, Alexander A1 - Dietrich, Lysanne Monika A1 - Humeniuk, Alexander A1 - Stolte, Matthias A1 - Schmidt, David A1 - Brixner, Tobias A1 - Würthner, Frank A1 - Mitric, Roland T1 - The origin of the solvent dependence of fluorescence quantum yields in dipolar merocyanine dyes JF - Chemical Science N2 - Fluorophores with high quantum yields are desired for a variety of applications. Optimization of promising chromophores requires an understanding of the non-radiative decay channels that compete with the emission of photons. We synthesized a new derivative of the famous laser dye 4-dicyanomethylen-2-methyl-6-p-dimethylaminostyryl-4H-pyran (DCM),i.e., merocyanine 4-(dicyanomethylene)-2-tert-butyl-6-[3-(3-butyl-benzothiazol-2-ylidene)1-propenyl]-4H-pyran (DCBT). We measured fluorescence lifetimes and quantum yields in a variety of solvents and found a trend opposite to the energy gap law.This motivated a theoretical investigation into the possible non-radiative decay channels. We propose that a barrier to a conical intersection exists that is very sensitive to the solvent polarity. The conical intersection is characterized by a twisted geometry which allows a subsequent photoisomerization. Transient absorption measurements confirmed the formation of a photoisomer in unpolar solvents, while the measurements of fluorescence quantum yields at low temperature demonstrated the existence of an activation energy barrier. KW - solvent-dependent fluorescence yield Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-198707 UR - https://doi.org/10.1039/C9SC05012D VL - 10 ER - TY - INPR A1 - Stennett, Tom E. A1 - Bissinger, Philipp A1 - Griesbeck, Stefanie A1 - Ullrich, Stefan A1 - Krummenacher, Ivo A1 - Auth, Michael A1 - Sperlich, Andreas A1 - Stolte, Matthias A1 - Radacki, Krzysztof A1 - Yao, Chang-Jiang A1 - Würthner, Frank A1 - Steffen, Andreas A1 - Marder, Todd B. A1 - Braunschweig, Holger T1 - Near-Infrared Quadrupolar Chromophores Combining Three-Coordinate Boron-Based Superdonor and Superacceptor Units T2 - Angewandte Chemie, International Edition N2 - In this work, two new quadrupolar A-π-D-π-A chromophores have been prepared featuring a strongly electron- donating diborene core and strongly electron-accepting dimesitylboryl F(BMes2) and bis(2,4,6-tris(trifluoromethyl)phenyl)boryl (BMes2) end groups. Analysis of the compounds by NMR spectroscopy, X-ray crystallography, cyclic voltammetry and UV-vis-NIR absorption and emission spectroscopy indicated that the compounds possess extended conjugated π-systems spanning their B4C8 cores. The combination of exceptionally potent π-donor (diborene) and π- acceptor (diarylboryl) groups, both based on trigonal boron, leads to very small HOMO-LUMO gaps, resulting in strong absorption in the near-IR region with maxima in THF at 840 and 1092 nm, respectively, and very high extinction coefficients of ca. 120,000 M-1cm-1. Both molecules also display weak near-IR fluorescence with small Stokes shifts. KW - boron KW - near-IR chromophores KW - conjugation KW - low-valent compounds KW - synthesis Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-180391 N1 - This is the pre-peer reviewed version of the following article: T. E. Stennett, P. Bissinger, S. Griesbeck, S. Ullrich, I. Krummenacher, M. Auth, A. Sperlich, M. Stolte, K. Radacki, C.-J. Yao, F. Wuerthner, A. Steffen, T. B. Marder, H. Braunschweig, Angew. Chem. Int. Ed. 2019, 58, 6449. , which has been published in final form at https://doi.org/10.1002/anie.201900889. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. ER - TY - JOUR A1 - He, Tao A1 - Stolte, Matthias A1 - Burschka, Christian A1 - Hansen, Nis Hauke A1 - Musiol, Thomas A1 - Kälblein, Daniel A1 - Pflaum, Jens A1 - Tao, Xutang A1 - Brill, Jochen A1 - Würthner, Frank T1 - Single-crystal field-effect transistors of new Cl\(_{2}\)-NDI polymorph processed by sublimation in air JF - Nature Communications N2 - Physical properties of active materials built up from small molecules are dictated by their molecular packing in the solid state. Here we demonstrate for the first time the growth of n-channel single-crystal field-effect transistors and organic thin-film transistors by sublimation of 2,6-dichloro-naphthalene diimide in air. Under these conditions, a new polymorph with two-dimensional brick-wall packing mode (\(\beta\)-phase) is obtained that is distinguished from the previously reported herringbone packing motif obtained from solution (\(\alpha\)-phase). We are able to fabricate single-crystal field-effect transistors with electron mobilities in air of up to 8.6 cm\(^{2}\)V\(^{-1}\)s\(^{-1}\) (\(\alpha\)-phase) and up to 3.5 cm\(^{2}\)V\(^{-1}\)s\(^{-1}\) (\(\beta\)-phase) on n-octadecyltriethoxysilane-modified substrates. On silicon dioxide, thin-film devices based on \(\beta\)-phase can be manufactured in air giving rise to electron mobilities of 0.37 cm\(^{2}\)V\(^{-1}\)s\(^{-1}\). The simple crystal and thin-film growth procedures by sublimation under ambient conditions avoid elaborate substrate modifications and costly vacuum equipment-based fabrication steps. KW - thin-film transistors KW - carrier transport KW - \(\beta\)-phase KW - organic semiconductors KW - induced phase transition KW - charge transport KW - materials design KW - \(\alpha\)-phase KW - mobility KW - pentacene Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-149255 VL - 6 IS - 5954 ER - TY - JOUR A1 - Müller, Ulrich A1 - Spenst, Peter A1 - Kagerer, Philipp A1 - Stolte, Matthias A1 - Würthner, Frank A1 - Pflaum, Jens T1 - Photon‐Correlation Studies on Multichromophore Macrocycles of Perylene Dyes JF - Advanced Optical Materials N2 - Organic dyes offer unique properties for their application as room temperature single photon emitters. By means of photon‐correlation, the emission characteristics of macrocyclic para‐xylylene linked perylene bisimide (PBI) trimers and tetramers dispersed in polymethyl methacrylate matrices are analyzed. The optical data indicate that, despite of the strong emission enhancement of PBI trimers and tetramers according to their larger number of chromophores, the photon‐correlation statistics still obeys that of single photon emitters. Moreover, driving PBI trimers and tetramers at higher excitation powers, saturated emission behavior for monomers is found while macrocycle emission is still far‐off saturation but shows enhanced fluctuations. This observation is attributed to fast singlet–singlet annihilation, i.e., faster than the radiative lifetime of the excited S1 state, and the enlarged number of conformational arrangements of multichromophores in the polymeric host. Finally, embedding trimeric PBI macrocycles in active organic light‐emitting diode matrices, electrically driven bright fluorescence together with an indication for antibunching at room temperature can be detected. This, so far, has only been observed for phosphorescent emitters that feature much longer lifetimes of the excited states and, thus, smaller radiative recombination rates. The results are discussed in the context of possible effects on the g(2) behavior of molecular emitters. KW - multichromophores KW - organic light emitting diodes KW - perylene dyes KW - photon‐correlation KW - single photon emission Y1 - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-287219 VL - 10 IS - 14 ER - TY - JOUR A1 - Kim, Jin Hong A1 - Schembri, Tim A1 - Bialas, David A1 - Stolte, Matthias A1 - Würthner, Frank T1 - Slip‐Stacked J‐Aggregate Materials for Organic Solar Cells and Photodetectors BT - This paper is dedicated to Prof. Daoben Zhu on the occasion of his 80th birthday JF - Advanced Materials N2 - Dye–dye interactions affect the optical and electronic properties in organic semiconductor films of light harvesting and detecting optoelectronic applications. This review elaborates how to tailor these properties of organic semiconductors for organic solar cells (OSCs) and organic photodiodes (OPDs). While these devices rely on similar materials, the demands for their optical properties are rather different, the former requiring a broad absorption spectrum spanning from the UV over visible up to the near‐infrared region and the latter an ultra‐narrow absorption spectrum at a specific, targeted wavelength. In order to design organic semiconductors satisfying these demands, fundamental insights on the relationship of optical properties are provided depending on molecular packing arrangement and the resultant electronic coupling thereof. Based on recent advancements in the theoretical understanding of intermolecular interactions between slip‐stacked dyes, distinguishing classical J‐aggregates with predominant long‐range Coulomb coupling from charge transfer (CT)‐mediated or ‐coupled J‐aggregates, whose red‐shifts are primarily governed by short‐range orbital interactions, is suggested. Within this framework, the relationship between aggregate structure and functional properties of representative classes of dye aggregates is analyzed for the most advanced OSCs and wavelength‐selective OPDs, providing important insights into the rational design of thin‐film optoelectronic materials. KW - crystal engineering KW - exciton coupling KW - J‐aggregates KW - organic photodiodes KW - organic solar cells Y1 - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-276537 VL - 34 IS - 22 ER - TY - JOUR A1 - Menekse, Kaan A1 - Renner, Rebecca A1 - Mahlmeister, Bernhard A1 - Stolte, Matthias A1 - Würthner, Frank T1 - Bowl-shaped naphthalimide-annulated corannulene as nonfullerene acceptor in organic solar cells JF - Organic Materials N2 - An electron-poor bowl-shaped naphthalimide-annulated corannulene with branched alkyl residues in the imide position was synthesized by a palladium-catalyzed cross-coupling annulation sequence. This dipolar compound exhibits strong absorption in the visible range along with a low-lying LUMO level at –3.85 eV, enabling n-type charge transport in organic thin-film transistors. Furthermore, we processed inverted bulk-heterojunction solar cells in combination with the two donor polymers PCE–10 and PM6 to achieve open-circuit voltages up to 1.04 V. By using a blend of the self-assembled naphthalimide-annulated corannulene and PCE–10, we were able to obtain a power conversion efficiency of up to 2.1%, which is to the best of our knowledge the highest reported value for a corannulene-based organic solar cell to date. KW - Chemie KW - corannulene KW - nonfullerene acceptors KW - curved π-systems KW - bulk-heterojunction solar cells KW - aggregation Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-299095 UR - https://www.thieme-connect.com/products/ejournals/html/10.1055/s-0040-1714283 SN - 2625-1825 VL - 2 IS - 3 ER - TY - JOUR A1 - Kim, Jin Hong A1 - Liess, Andreas A1 - Stolte, Matthias A1 - Krause, Ana-Maria A1 - Stepanenko, Vladimir A1 - Zhong, Chuwei A1 - Bialas, David A1 - Spano, Frank A1 - Würthner, Frank T1 - An Efficient Narrowband Near-Infrared at 1040 nm Organic Photodetector Realized by Intermolecular Charge Transfer Mediated Coupling Based on a Squaraine Dye JF - Advanced Materials N2 - A highly sensitive short-wave infrared (SWIR, λ > 1000 nm) organic photodiode (OPD) is described based on a well-organized nanocrystalline bulk-heterojunction (BHJ) active layer composed of a dicyanovinyl-functionalized squaraine dye (SQ-H) donor material in combination with PC\(_{61}\)BM. Through thermal annealing, dipolar SQ-H chromophores self-assemble in a nanoscale structure with intermolecular charge transfer mediated coupling, resulting in a redshifted and narrow absorption band at 1040 nm as well as enhanced charge carrier mobility. The optimized OPD exhibits an external quantum efficiency (EQE) of 12.3% and a full-width at half-maximum of only 85 nm (815 cm\(^{-1}\)) at 1050 nm under 0 V, which is the first efficient SWIR OPD based on J-type aggregates. Photoplethysmography application for heart-rate monitoring is successfully demonstrated on flexible substrates without applying reverse bias, indicating the potential of OPDs based on short-range coupled dye aggregates for low-power operating wearable applications. KW - squaraine dyes KW - crystal engineering KW - J-aggregates KW - near-infrared sensitivity KW - organic photodiodes Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256374 VL - 33 IS - 26 ER - TY - JOUR A1 - Peseschkian, Tara A1 - Cordts, Isabell A1 - Günther, René A1 - Stolte, Benjamin A1 - Zeller, Daniel A1 - Schröter, Carsten A1 - Weyen, Ute A1 - Regensburger, Martin A1 - Wolf, Joachim A1 - Schneider, Ilka A1 - Hermann, Andreas A1 - Metelmann, Moritz A1 - Kohl, Zacharias A1 - Linker, Ralf A. A1 - Koch, Jan Christoph A1 - Büchner, Boriana A1 - Weiland, Ulrike A1 - Schönfelder, Erik A1 - Heinrich, Felix A1 - Osmanovic, Alma A1 - Klopstock, Thomas A1 - Dorst, Johannes A1 - Ludolph, Albert C. A1 - Boentert, Matthias A1 - Hagenacker, Tim A1 - Deschauer, Marcus A1 - Lingor, Paul A1 - Petri, Susanne A1 - Schreiber-Katz, Olivia T1 - A nation-wide, multi-center study on the quality of life of ALS patients in Germany JF - Brain Sciences N2 - Improving quality of life (QoL) is central to amyotrophic lateral sclerosis (ALS) treatment. This Germany-wide, multicenter cross-sectional study analyses the impact of different symptom-specific treatments and ALS variants on QoL. Health-related QoL (HRQoL) in 325 ALS patients was assessed using the Amyotrophic Lateral Sclerosis Assessment Questionnaire 5 (ALSAQ-5) and EuroQol Five Dimension Five Level Scale (EQ-5D-5L), together with disease severity (captured by the revised ALS Functional Rating Scale (ALSFRS-R)) and the current care and therapies used by our cohort. At inclusion, the mean ALSAQ-5 total score was 56.93 (max. 100, best = 0) with a better QoL associated with a less severe disease status (β = −1.96 per increase of one point in the ALSFRS-R score, p < 0.001). “Limb-onset” ALS (lALS) was associated with a better QoL than “bulbar-onset” ALS (bALS) (mean ALSAQ-5 total score 55.46 versus 60.99, p = 0.040). Moreover, with the ALSFRS-R as a covariate, using a mobility aid (β = −7.60, p = 0.001), being tracheostomized (β = −14.80, p = 0.004) and using non-invasive ventilation (β = −5.71, p = 0.030) were associated with an improved QoL, compared to those at the same disease stage who did not use these aids. In contrast, antidepressant intake (β = 5.95, p = 0.007), and increasing age (β = 0.18, p = 0.023) were predictors of worse QoL. Our results showed that the ALSAQ-5 was better-suited for ALS patients than the EQ-5D-5L. Further, the early and symptom-specific clinical management and supply of assistive devices can significantly improve the individual HRQoL of ALS patients. Appropriate QoL questionnaires are needed to monitor the impact of treatment to provide the best possible and individualized care. KW - Amyotrophic Lateral Sclerosis (ALS) KW - Amyotrophic Lateral Sclerosis Assessment Questionnaire 5 (ALSAQ-5) KW - ALS treatment KW - “bulbar-onset” ALS (bALS) KW - “limb-onset” ALS (lALS) KW - EuroQol Five Dimension Five Level Scale (EQ-5D-5L) KW - health-related quality of life (HRQoL) KW - quality of life (QoL) KW - symptom-specific treatment KW - assistive devices Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-234147 SN - 2076-3425 VL - 11 IS - 3 ER - TY - JOUR A1 - Brust, Felix A1 - Nagler, Oliver A1 - Shoyama, Kazutaka A1 - Stolte, Matthias A1 - Würthner, Frank T1 - Organic Light‐Emitting Diodes Based on Silandiol‐Bay‐Bridged Perylene Bisimides JF - Advanced Optical Materials N2 - Perylene bisimides (PBIs) are among the best fluorophores but have to be enwrapped for optoelectronic applications by large and heavy substituents to prevent their ππ‐stacking, which is known to accelerate non‐radiative decay processes in the solid state. Here, light‐weight di‐tert‐butylsilyl groups are introduced to bridge 1,12‐dihydroxy and 1,6,7,12‐tetrahydroxy PBIs to afford sublimable dyes for vacuum‐processed optoelectronic devices. For both new compounds, this substitution provides a twisted and shielded perylene π‐core whose, via OSiObridges, rigid structure affords well‐resolved absorption and emission spectra with strong fluorescence in solution, as well as in the solid state. The usefulness of these dyes for vacuum‐processed optoelectronic devices is demonstrated in organic light‐emitting diodes (OLEDs) that show monomer‐like emission spectra and high maximum external quantum efficiency (EQEmax) values of up to 3.1% for the doubly silicon‐bridged PBI. KW - organic light emitting diodes KW - perylene bisimide dyes KW - rigidification KW - solid‐state emission KW - vacuum processable Y1 - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-312599 VL - 11 IS - 5 ER -