State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China.
Chemistry. 2011 Aug 1;17(32):8965-83. doi: 10.1002/chem.201002596. Epub 2011 Jun 16.
The successful synthesis of tetraphenyltetraphenanthroporphyrin (TPTPhenP; 5a) in 2006 under modified Rothemund-Lindsey conditions yielded a tetraphenyl porphyrinoid with a B band redshifted to an unprecedented 576 nm. Radially symmetric fused-ring expansion of tetraphenylporphyrin with phenanthrene moieties results in very deep saddling due to steric crowding and very marked redshifts of the Q and B (or Soret) porphyrinoid absorption bands. The extent to which the TPTPhenP structure can be further modified is explored, and the optical properties of TPTPhenPs are analyzed based on a perimeter model approach that makes use of time-dependent DFT calculations and magnetic circular dichroism spectroscopy and also based on a detailed analysis of the fluorescence emission. Attempts to introduce substituents at the ortho and meta positions of the meso-phenyl groups and to insert a central metal proved unsuccessful. The synthesis of a series of TPTPhenPs with strong electron-withdrawing (-CN, -NO(2)) and -donating (-CH(3), -N(CH(3))(2)) substituents at the para positions of the meso-phenyl rings is reported. Marked redshifts of the main spectral bands were consistently observed. The most pronounced spectral changes were observed with -N(CH(3))(2) groups (5i) due to a marked destabilization of the HOMO, which has large MO coefficients on the meso-carbon atoms. Protonation of 5i at both the ligand core and at the -N(CH(3))(2) groups resulted in unprecedented Q(00) band absorption at wavelengths greater than 1200 nm.
2006 年，在改良的 Rothemund-Lindsey 条件下成功合成了四苯基四苯并卟啉（TPTPhenP；5a），得到了一个 B 带红移至前所未有的 576nm 的四苯基卟啉类化合物。由于空间拥挤，与菲并苯部分的四苯基卟啉的径向对称融合环扩展导致非常深的鞍点，并且 Q 和 B（或 Soret）卟啉类吸收带的红移非常显著。进一步探讨了 TPTPhenP 结构可以进一步修饰的程度，并基于周长模型方法分析了 TPTPhenP 的光学性质，该方法利用了时间依赖的 DFT 计算和磁圆二色性光谱，并且还基于对荧光发射的详细分析。尝试在间位苯基的邻位和间位引入取代基以及插入中心金属的尝试均未成功。报道了一系列具有强吸电子（-CN，-NO2）和供电子（-CH3，-N（CH3）2）取代基的 TPTPhenP 的合成。一致观察到主要光谱带的明显红移。带有-N（CH3）2 取代基的化合物（5i）观察到最显著的光谱变化，这是由于 HOMO 的明显失稳，其在间位碳原子上具有较大的 MO 系数。5i 在配体核心和-N（CH3）2 基团上的质子化导致在大于 1200nm 的波长处出现前所未有的 Q（00）带吸收。
