期刊
INORGANIC CHEMISTRY
卷 60, 期 7, 页码 5391-5401出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c00416
关键词
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资金
- Baden-Wurttemberg Foundation (BW-Stiftung, Germany)
- Deutsche Forschungsgemeinschaft (DFG) [SPP 2102, TS 330/4-1, KA 4671/2-1]
- DFG [INST 40/467-1 FUGG, TS 330/3-1]
- state of Baden-Wurttemberg through bwHPC
This study extended the backbone of 2,9-dimethyl-1,10-phenanthroline to develop novel heteroleptic Cu(I) complexes with various substituents using specialized cross-coupling reactions. The substituents were found to influence the optical properties and electrochemical properties of the complexes, with alkynyl-based complexes showing red-shifted absorption maxima and increased absorptivity, and phenyl-based complexes affecting emission wavelength and quantum yield.
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)]PF6.
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