Low-Temperature Observation of the Excited-State Decay of Ruthenium-(Mono-2,2?:6?,2?-Terpyridine) Ions with Innocent Ligands: DFT Modeling of an 3MLCT-3MC Intersystem Crossing Pathway

被引：5

作者：

Yin, Chi-Wei ^{[1
]}

Tsai, Ming-Kang ^{[1
,2
]}

Chen, Yuan Jang ^{[1
]}

机构：

[1] Fu Jen Catholic Univ, Dept Chem, New Taipei 24205, Taiwan

[2] Natl Taiwan Normal Univ, Dept Chem, Taipei 11677, Taiwan

来源：

ACS OMEGA | 2023年 / 8卷 / 12期

关键词：

TRANSITION-METAL-COMPLEXES; PHOTOPHYSICAL PROPERTIES; QUANTUM EFFICIENCIES; ELECTRON-TRANSFER; RU(II) COMPLEXES; RUTHENIUM(II); ENERGY; EXCHANGE; APPROXIMATION; LUMINESCENCE;

D O I：

10.1021/acsomega.3c01006

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The synthesis, electrochemistry, and photophysical characterization of five 2,2 ':6 ',2 ''-terpyridine ruthenium complexes (Ru-tpy complexes) is reported. The electrochemical and photophysical behavior varied depending on the ligands, i.e., amine (NH3), acetonitrile (AN), and bis(pyrazolyl)methane (bpm), for this series of Ru-tpy complexes. The target [Ru(tpy)(AN)3]2+ and [Ru(tpy)(bpm)(AN)]2+ complexes were found to have low-emission quantum yields in low temperature observations. To better understand this phenomenon, density functional theory (DFT) calculations were performed to simulate the singlet ground state (S0), Te, and metal-centered excited states (3MC) of these complexes. The calculated energy barriers between Te and the low-lying 3MC state for [Ru(tpy)(AN)3]2+ and [Ru(tpy)(bpm)(AN)]2+ provided clear evidence in support of their emitting state decay behavior. Developing a knowledge of the underlying photophysics of these Ru-tpy complexes will allow new complexes to be designed for use in photophysical and photochemical applications in the future.

引用

页码：11623 / 11633

页数：11