Influence of nonplanarity and extended conjugation on porphyrin basicity

被引：68

作者：

Finikova, OS

Cheprakov, AV ^{[1
]}

Carroll, PJ

Dalosto, S

Vinogradov, SA

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119899, Russia

[2] Univ Penn, Dept Chem, Crystallog Lab, Philadelphia, PA 19104 USA

[3] Univ Penn, Dept Biochem & Biophys, Philadelphia, PA 19104 USA

来源：

INORGANIC CHEMISTRY | 2002年 / 41卷 / 26期

关键词：

D O I：

10.1021/ic0260522

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Thermodynamic basicities of several new nonplanar water soluble tetraaryltetracyclohexano- (Ar4TCHP) and tetraaryltetrabenzoporphyrins (Ar4TBP) have been measured and correlated with their structural parameters. While the degrees of nonplanarity in these porphyrins are similar, Ar(4)TCHPs exhibit significantly higher basicities than Ar(4)TBPs and than planar tetraarylporphyrins. Low basicities of distorted Ar(4)TBPs are believed to be due to extended pi-conjugation, which causes delocalization of the core electron density in these porphyrins and reduces negative charges at the protonation site.

引用

页码：6944 / 6946

页数：3

共 22 条

[11] Modification of the porphyrin chromophore by ring fusion: identifying trends due to annelation of the porphyrin nucleus [J].