Wössner Jan S, Esser Birgit
Institute for Organic Chemistry, University of Freiburg, Albertstraße 21, 79104 Freiburg, Germany.
Freiburg Materials Research Center, University of Freiburg, Stefan-Meier-Straße 21, 79104 Freiburg, Germany.
J Org Chem. 2020 Apr 3;85(7):5048-5057. doi: 10.1021/acs.joc.0c00567. Epub 2020 Mar 26.
Charge-transfer-based materials with intramolecular donor-acceptor structures are attractive for technological applications. Herein, a series of donor-σ-acceptor dyes has been prepared in a modular approach. The design of these intramolecular charge-transfer dyes is based on the concept of spiroconjugation, which leads to unique materials with special optical properties. The optical transitions are based on intramolecular charge transfer, as shown by solvatochromic measurements and density functional theory (DFT) calculations. Crystallographic, computational, electrochemical, and optical studies were performed to clarify the effect of different perpendicular π-moieties on the optoelectronic properties. Our molecular tuning allowed for the synthesis of molecules exhibiting strong visible-range absorption. The compounds are not fluorescent due to structural changes in the excited state, as revealed by DFT calculations. Finally, our study describes enantiomerically pure spiroconjugated absorber molecules using 1,1'-binaphthyl-2,2'-diol (BINOL) units on the donor part.
具有分子内供体-受体结构的基于电荷转移的材料在技术应用方面具有吸引力。在此，通过模块化方法制备了一系列供体-σ-受体染料。这些分子内电荷转移染料的设计基于螺共轭概念，这导致了具有特殊光学性质的独特材料。如溶剂化显色测量和密度泛函理论（DFT）计算所示，光学跃迁基于分子内电荷转移。进行了晶体学、计算、电化学和光学研究，以阐明不同垂直π-基团对光电性质的影响。我们的分子调控使得能够合成出在可见光范围内具有强烈吸收的分子。正如DFT计算所揭示的，由于激发态的结构变化，这些化合物不具有荧光性。最后，我们的研究描述了在供体部分使用1,1'-联萘-2,2'-二醇（BINOL）单元的对映体纯螺共轭吸收分子。
