Department of Pharmaceutical Chemistry and Drug Control, Faculty of Pharmacy in Hradec Kralove, Charles University in Prague, Heyrovskeho 1203, 50005, Hradec Kralove, Czech Republic.
Dalton Trans. 2012 Oct 14;41(38):11651-6. doi: 10.1039/c2dt31403g. Epub 2012 Jul 26.
Intramolecular charge transfer (ICT) was studied on a series of magnesium, metal-free and zinc complexes of unsymmetrical tetrapyrazinoporphyrazines and tribenzopyrazinoporphyrazines bearing two dialkylamino substituents (donors) and six alkylsulfanyl or aryloxy substituents (non-donors). The dialkylamino substituents were responsible for ICT that deactivated excited states and led to considerable decrease of fluorescence and singlet oxygen quantum yields. Photophysical and photochemical properties were compared to corresponding macrocycles that do not bear any donor centers. The data showed high feasibility of ICT in the tetrapyrazinoporphyrazine macrocycle and significantly lower efficiency of this deactivation process in the tribenzopyrazinoporphyrazine type molecules. Considerable effect of non-donor peripheral substituents on ICT was also described. The results imply that tetrapyrazinoporphyrazines may be more suitable for development of new molecules investigated in applications based on ICT.
研究了一系列具有不对称四吡嗪卟啉和三苯并吡嗪卟啉结构的镁、无金属和锌配合物，这些配合物带有两个二烷基氨基取代基（给体）和六个烷基硫代或芳氧基取代基（非给体）。二烷基氨基取代基负责发生引起激发态失活的分子内电荷转移（ICT），导致荧光和单线态氧量子产率显著降低。将光物理和光化学性质与不带有任何给体中心的相应大环进行了比较。数据表明，ICT 在四吡嗪卟啉大环中具有很高的可行性，而在三苯并吡嗪卟啉型分子中，这种失活过程的效率要低得多。还描述了非给体外围取代基对 ICT 的显著影响。结果表明，四吡嗪卟啉可能更适合于基于 ICT 的应用中研究的新型分子的开发。
