化学
卟啉
吡咯
双金属片
共轭体系
吸收(声学)
结晶学
产量(工程)
吸收光谱法
金属
光化学
立体化学
有机化学
聚合物
物理
冶金
材料科学
量子力学
声学
作者
Zhen Yang,Glib Baryshnikov,Feng Sha,Chengjie Li,Xinyan Wu,Hans Agren,Yongshu Xie,Qizhao Li
标识
DOI:10.1142/s1088424622500985
摘要
A hexapyrrane P6with a terminal N-confused pyrrole was synthesized by acid-catalyzed [3+3] condensation followed by oxidation with DDQ, which did not afford the expected N-confused hexaphyrin. In stead, a rearranged product, [Formula: see text], [Formula: see text]-dipyrrin appended N-confused porphyrin 1 was obtained in a yield of 46%. Chelation of 1 with Pt(II) afforded the peripheral complex 1-Pt, which was further coordinated with Rh(I) in the cavity to afford the corresponding bimetallic complex 1-Pt-Rh. Both 1-Pt and 1-Pt-Rh exhibit split Soret-like bands and noticeable Q-like bands tailing to the NIR region up to ca. 1200 nm. Single crystal X-ray diffraction analyses of 1 and 1-Pt revealed that the peripheral coordination of Pt(II) slightly modifies the interplanar angle between the porphyrin macrocycle and the dipyrrin unit, which may modulate the absorption spectra. The results of this work compose an interesting example of synthesizing porphyrinoids appended with conjugated peripheral chains by the oxidative ring closure reaction of an oligopyrrane containing a terminal N-confused pyrrole, and such compounds may be used for both inner and peripheral coordination to afford complexes with tunable NIR absorption.
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