Theoretical Analysis on Molecular Magnetic Properties of N-Confused Porphyrins and Its Derivatives

Bulletin of the Korean chemical society

Fu-Quan Bai¹  Bao-Hui Xia¹  Wei Wei¹  Hong-Xing Zhang¹ 

关键词: Heteroporphyins;    Hetero-N-confused porphyrins;    NICS;    π current density;    1H NMR;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

We have theoretically investigated the magnetic properties of N-confused porphyrin (NCP), tetraphenyl-Nconfused porphyrin (TPNCP) and their substituted derivatives with O, S and Se heteroatoms (2ONCP, 2STPNCP, 2SeNCP, 2OTPNCP, etc.) by using DFT method. In the minimum energy structures of the 2OTPNCP, the two couples opposite phenyl substitutes are staggered. In the case of TPNCP, 2STPNCP and 2SeTPNCP, two phenyls being respectively close to or opposite to N-confused pyrrole are found to be pointed the same direction, whilst others are in the opposite direction. Based on the equilibrium structures, the 1H chemical shifts and nucleus-independent chemical shifts (NICS) are calculated in this paper. The π current density being induced by the tridimensional perpendicular magnetic field transmits the inner section of the pyrrole segments for NCP and TPNCP. As for their substituted derivatives with O, S and Se atoms, the current path passes through the outer section of the two heterorings. The NICS values at the ring critical points of the heterorings are much lower (in absolute value) than those of which is at the center of an isolated pyrrole molecule. The 1H NMR for β H atoms of the heterorings decreases from O, S to with Se.

【 授权许可】

Unknown