Dual Emission Caused by Ring Inversion Isomerization of a 4-Methyl-2-pyridyl-pyrimidine Copper(I) Complex

被引：73

作者：

Nishikawa, Michihiro ^{[1
]}

Nomoto, Kuniharu ^{[1
]}

Kume, Shoko ^{[1
]}

Inoue, Keiichi ^{[1
]}

Sakai, Makoto ^{[1
]}

Fujii, Masaaki ^{[1
]}

Nishihara, Hiroshi ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Sci, Dept Chem, Bunkyo Ku, Tokyo 1130033, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 28期

关键词：

CU(I); DEVICES; LIGAND;

D O I：

10.1021/ja103718e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We developed a new convertible copper(I) complex using 2-pyridyl-4-methylpyrimidine and diphosphine as ligands. This complex exhibited mechanical bistability based on the inversion motion of the pyrimidine ring, leading to dual luminescence behavior. The inversion dynamics was strongly dependent on temperature and solvent. Variable-temperature H-1 NMR spectra revealed that the two isomers interconverted in solution via ring inversion, and the motion was frozen below 200 K. The complex exhibited characteristic CT absorption and emission bands in solution. Emission lifetime measurements demonstrated that the emission could be deconvoluted into two components. The fast and slow components were assigned to the two isomers, the excited states of which were characterized by different structural relaxation process and/or additional solvent coordination properties. The emission properties of the two isomers differed not only in lifetime and wavelength but also in heat sensitivity. The molar ratio of the two isomers varied with the polarity of the solvent via electrostatic interactions with the counteranion. The rate of inversion was affected by solvent, suggesting that inversion was promoted by solvent coordination.

引用

页码：9579 / 9581

页数：3

共 22 条

[1] Photodriven heterogeneous charge transfer with transition-metal compounds anchored to TiO2 semiconductor surfaces [J].

Ardo, Shane ;

Meyer, Gerald J. .

CHEMICAL SOCIETY REVIEWS, 2009, 38 (01) :115-164

[2] Photochemistry and photophysics of coordination compounds: Copper [J].

Armaroli, Nicola ;

Accorsi, Gianluca ;

Cardinali, Francois ;

Listorti, Andrea .

PHOTOCHEMISTRY AND PHOTOPHYSICS OF COORDINATION COMPOUNDS I, 2007, 280 :69-115

[3] High-efficiency fluorescent organic light-emitting devices using a phosphorescent sensitizer [J].

Baldo, MA ;

Thompson, ME ;

Forrest, SR .

NATURE, 2000, 403 (6771) :750-753

[4] Highly efficient phosphorescent emission from organic electroluminescent devices [J].

Baldo, MA ;

O'Brien, DF ;

You, Y ;

Shoustikov, A ;

Sibley, S ;

Thompson, ME ;

Forrest, SR .

NATURE, 1998, 395 (6698) :151-154

[5] Making Oxygen with Ruthenium Complexes [J].

Concepcion, Javier J. ;

Jurss, Jonah W. ;

Brennaman, M. Kyle ;

Hoertz, Paul G. ;

Patrocinio, Antonio Otavio T. ;

Murakami Iha, Neyde Yukie ;

Templeton, Joseph L. ;

Meyer, Thomas J. .

ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (12) :1954-1965

[6] Simple Cu(I) complexes with unprecedented excited-state lifetimes [J].

Cuttell, DG ;

Kuang, SM ;

Fanwick, PE ;

McMillin, DR ;

Walton, RA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (01) :6-7

[7]

DeAmond M. K., 1981, COORDIN CHEM REV, V36, P325

[8] Coordination complexes exhibiting room-temperature phosphorescence: Evaluation of their suitability as triplet emitters in organic light emitting diodes [J].

Evans, Rachel C. ;

Douglas, Peter ;

Winscom, Christopher J. .

COORDINATION CHEMISTRY REVIEWS, 2006, 250 (15-16) :2093-2126

[9] Ruthenium complexes that break the rules: Structural features controlling dual emission [J].

Glazer, Edith C. ;

Magde, Douglas ;

Tor, Yitzhak .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (27) :8544-8551

[10] Molecular photovoltaics [J].

Hagfeldt, A ;

Grätzel, M .

ACCOUNTS OF CHEMICAL RESEARCH, 2000, 33 (05) :269-277

← 1 2 3 →