Synthesis and characterization of optically active and racemic forms of cyclometalated Rh(III) complexes. An experimental and theoretical emission study

被引：35

作者：

Ghizdavu, L ^{[1
]}

Lentzen, O ^{[1
]}

Schumm, S ^{[1
]}

Brodkorb, A ^{[1
]}

Moucheron, C ^{[1
]}

Kirsch-De Mesmaeker, A ^{[1
]}

机构：

[1] Free Univ Brussels, B-1050 Brussels, Belgium

来源：

INORGANIC CHEMISTRY | 2003年 / 42卷 / 06期

关键词：

D O I：

10.1021/ic020435i

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The optically active cyclometalated Rh(III) complexes, Delta[Rh(thpy4,5p(RR)PY)(2)TAP]CI, Lambda[Rh(thpy4,5p(S,S)py)(2)TAP]-Cl, and Delta[Rh(phpy4,5p(RR)py)(2)TAP]CI (where TAP = 1,4,5,8-tetraazaphenanthrene, thpy4,5p(RR)py = (8R,10R)-2-(2'-thienyl)-4,5-pinenopyridine and phpy4,5p(RR)py = (8R,10R)-2-(2'-phenyl)-4,5-pinenopyridine) have been prepared and characterized. Their photophysics has been examined in parallel with that of rac[Rh(thPY)(2)TAP]CI and rac[Rh(phpy)(2)TAP]Cl. Their behaviors have been rationalized from results of TD-DFT calculations. The complexes with thienylpyridine (thpy) as cyclometalating ligands exhibit (CT)-C-3 (from thpy to TAP) and (LCpi-pi)-L-3 (centered on thpy) emissions in a solvent matrix at 77 K and one (CT)-C-3 luminescence at room temperature. In contrast, with phenylpyridine (phpy), the complexes show only one (CT)-C-3 emission (from phpy to TAP) at both temperatures.

引用

页码：1935 / 1944

页数：10

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