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  - Zhang, Fangyuan
A1  - Radacki, Krzysztof
A1  - Braunschweig, Holger
A1  - Lambert, Christoph
A1  - Ravat, Prince
T1  - Zinc-[7]helicenocyanine and its discrete π-stacked homochiral Dimer
JF  - Angewandte Chemie International Edition
N2  - In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene-Pc hybrid molecular structure, zinc-[7]helicenocyanine (Zn-7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×10\(^6\) M\(^{−1}\) and 3.42×107 M\(^{−1}\) in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn\(^{-7}\)HPc exhibited chiral self-sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV-CT band for the thermodynamically stable mixed-valence state.
KW  - organic chemistry
KW  - supramolecular assembly
KW  - chirality
KW  - helicenes
KW  - homochiral dimer
KW  - phthalocyanines
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256534
VL  - 60
ER  - 
TY  - JOUR
A1  - Full, Felix
A1  - Wölflick, Quentin
A1  - Radacki, Krzysztof
A1  - Braunschweig, Holger
A1  - Nowak‐Król, Agnieszka
T1  - Enhanced Optical Properties of Azaborole Helicenes by Lateral and Helical Extension
JF  - Chemistry – A European Journal
N2  - The synthesis and characterization of laterally extended azabora[5]‐, ‐[6]‐ and ‐[7]helicenes, assembled from N‐heteroaromatic and dibenzo[g,p]chrysene building blocks is described. Formally, the π‐conjugated systems of the pristine azaborole helicenes were enlarged with a phenanthrene unit leading to compounds with large Stokes shifts, significantly enhanced luminescence quantum yields (Φ) and dissymmetry factors (g\(_{lum}\)). The beneficial effect on optical properties was also observed for helical elongation. The combined contributions of lateral and helical extensions resulted in a compound showing green emission with Φ of 0.31 and |g\(_{lum}\)| of 2.2×10\(^{−3}\), highest within the series of π‐extended azaborahelicenes and superior to emission intensity and chiroptical response of its non‐extended congener. This study shows that helical and lateral extensions of π‐conjugated systems are viable strategies to improve features of azaborole helicenes. In addition, single crystal X‐ray analysis of configurationally stable [6]‐ and ‐[7]helicenes was used to provide insight into their packing arrangements.
KW  - azaborole
KW  - circularly polarized luminescence
KW  - fluorescence
KW  - helicene
KW  - π-extension
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-293671
VL  - 28
IS  - 62
ER  -