Doettinger Florian, Yang Yingya, Schmid Marie-Ann, Frey Wolfgang, Karnahl Michael, Tschierlei Stefanie
Institute of Organic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
Department of Energy Conversion, Institute of Physical and Theoretical Chemistry, Technische Universität Brauschweig, Gaußstraße 17, 38106 Braunschweig, Germany.
Inorg Chem. 2021 Apr 5;60(7):5391-5401. doi: 10.1021/acs.inorgchem.1c00416. Epub 2021 Mar 25.
With the aims of increasing the antenna system and improving the photophysical properties of Cu(I)-based photosensitizers, the backbone of 2,9-dimethyl-1,10-phenanthroline was selectively extended in the 5,6-position. Applying specifically tailored Suzuki-Miyaura and "chemistry-on-the-complex" Sonogashira cross-coupling reactions enabled the development of two sets of structurally related diimine ligands with a broad variety of different phenyl- and alkynyl-based substituents. The resulting 11 novel heteroleptic Cu(I) complexes, including five solid-state structures, were studied with respect to their structure-property relationships. Both sets of substituents are able to red-shift the absorption maxima and to increase the absorptivity. For the alkynyl-based complexes, this is accompanied by a significant anodic shift of the reduction potentials. The phenyl-based substituents strongly influence the emission wavelength and quantum yield of the resulting Cu(I) complexes and lead to an increase in the emission lifetime of up to 504 ns, which clearly indicates competition with the benchmark system [(xantphos)Cu(bathocuproine)]PF.
为了增加天线系统并改善基于Cu(I)的光敏剂的光物理性质，2,9-二甲基-1,10-菲咯啉的主链在5,6位被选择性地延长。应用特别定制的铃木-宫浦和“配合物上的化学”Sonogashira交叉偶联反应，能够开发出两组具有多种不同苯基和炔基取代基的结构相关的二亚胺配体。研究了所得的11种新型杂配Cu(I)配合物，包括五种固态结构，探讨了它们的结构-性质关系。两组取代基都能够使吸收最大值发生红移并增加吸光度。对于基于炔基的配合物，这伴随着还原电位的显著阳极移动。基于苯基的取代基强烈影响所得Cu(I)配合物的发射波长和量子产率，并导致发射寿命增加至504 ns，这清楚地表明与基准体系[(xantphos)Cu(bathocuproine)]PF存在竞争。
