State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, PR China.
Chemistry. 2012 Dec 21;18(52):16844-67. doi: 10.1002/chem.201200956. Epub 2012 Nov 13.
The synthesis of a series of novel core-modified and fused-ring-expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem-crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine-tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso-phenyl rings, is also examined.
本文报道了一系列新型核心修饰和稠环扩展四苯并卟啉的合成。通过理论计算和磁圆二色（MCD）和荧光光谱测量分析了用第 16 族氧、硫、硒和碲原子对卟啉光学性质和电子结构的核心修饰的影响。观察到 Q 和 B 带的明显红移和加速的系间窜越速率，从而使这些化合物在各种应用中具有潜在的适用性。通过进一步的结构修饰（例如使用带有稠合双环[2.2.2]辛二烯环的噻吩前体来形成 ABAB 结构并在间-苯基环上引入各种取代基）进一步调整这些光学性质的范围也进行了研究。
