Pushpanandan Poornenth, Maurya Yogesh Kumar, Omagari Toshihiro, Hirosawa Ryuji, Ishida Masatoshi, Mori Shigeki, Yasutake Yuhsuke, Fukatsu Susumu, Mack John, Nyokong Tebello, Furuta Hiroyuki
Department of Chemistry and Biochemistry, Graduate School of Engineering and Center for Molecular Systems, Kyushu University , Fukuoka 819-0395, Japan.
Advanced Research Support Center, Ehime University , Matsuyama 790-8577, Japan.
Inorg Chem. 2017 Oct 16;56(20):12572-12580. doi: 10.1021/acs.inorgchem.7b02047. Epub 2017 Oct 2.
Organoplatinum(II) complexes of calix[4]phyrin analogues, singly N-confused calix[4]phyrin (Pt-2), and doubly N-confused calix[4]phyrin (Pt-3), were synthesized and characterized. The explicit structures of these organoplatinum(II) complexes were elucidated by single-crystal X-ray diffraction and spectroscopic studies. The introduction of N-confused pyrrole rings to the parent calix[4]phyrin scaffold was found to have profound effects on the photophysical properties, such as the bathochromic shifts of both the absorption and phosphorescence maxima. The triplet excited state properties of these platinum complexes were analyzed by DFT calculations at the B3LYP level. The organoplatinum(II) complexes derived from the deformed scaffolds can serve as potent triplet sensitizers for singlet oxygen generation under aerobic conditions.
合成并表征了杯[4]卟啉类似物、单N-稠合杯[4]卟啉（Pt-2）和双N-稠合杯[4]卟啉（Pt-3）的有机铂（II）配合物。通过单晶X射线衍射和光谱研究阐明了这些有机铂（II）配合物的明确结构。发现将N-稠合吡咯环引入母体杯[4]卟啉支架对光物理性质有深远影响，例如吸收和磷光最大值的红移。在B3LYP水平上通过DFT计算分析了这些铂配合物的三重激发态性质。源自变形支架的有机铂（II）配合物可作为在有氧条件下产生单线态氧的有效三重态敏化剂。
