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Meso-aryl phenanthroporphyrins: Synthesis and spectroscopic properties

机译：介芳芳基卟啉：合成与光谱性质

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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.
机译：2006年在改良的Rothemund-Lindsey条件下成功合成了四苯基四氮杂卟啉（TPTPhenP; 5a），产生了四苯基卟啉类化合物，其B波段红移至前所未有的576 nm。带有菲部分的四苯基卟啉的径向对称的稠环扩环由于空间拥挤以及Q和B（或Soret）卟啉类化合物吸收带的明显红移而导致非常深的鞍形。探索了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TPTPhenPs的光学性质，该方法利用了与时间有关的DFT计算和磁圆二色性光谱，并且还基于荧光发射。试图在内苯基的邻位和间位引入取代基并插入中心金属的尝试均未成功。报道了一系列在中苯环对位具有强吸电子（-CN，-NO_2）和-给体（-CH_3，-N（CH_3）_2）取代基的TPTPhenPs的合成。始终观察到主要光谱带明显的红移。由于HOMO的明显失稳，在-N（CH_3）_2基团（5i）上观察到最明显的光谱变化，而HOMO在中碳原子上具有较大的MO系数。在配体核心和-N（CH_3）_2基团上5i的质子化导致在大于1200 nm的波长下空前的Q_（00）吸收带。

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