Remote modulation of singlet-triplet gaps in carbenes

被引：4

作者：

Alkorta, Ibon ^{[1
]}

Merced Montero-Campillo, M. ^{[1
]}

Elguero, Jose ^{[1
]}

机构：

[1] CSIC, Inst Quim Med, Juan de la Cierva 3, E-28006 Madrid, Spain

来源：

CHEMICAL PHYSICS LETTERS | 2018年 / 694卷

关键词：

AB-INITIO; BONDED COMPLEXES; PI-NUCLEOPHILES; SPIN-STATE; DIPHENYLCARBENE; DERIVATIVES;

D O I：

10.1016/j.cplett.2018.01.039

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The modulation of the singlet-triplet (S/T) gap of phenyl-carbene derivatives by hydrogen bond formation has been studied using the G4(MP2) computational method. The complexation of the aromatic ring substituents (-NH2, -OH, -PH2, -SH) in meta-and para-positions with water and the protonation or deprotonation of such groups have a remarkable influence on the S/T gaps, reaching S/T gap variations from 25.7 to 93.7 kJ mol(-1). This variation is linearly related to the binding energy difference of the S/T configurations. Importantly, the triplet and singlet electronic configurations are systematically favored in the protonated and deprotonated forms, respectively, in all cases. (C) 2018 Elsevier B.V. All rights reserved.

引用

页码：48 / 52

页数：5

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