Synthesis and characterization of regioselective substituted tetrapyridophenazine ligands and their Ru(II) complexes

被引：44

作者：

Karnahl, Michael ^{[2
]}

Tschierlei, Stefanie ^{[1
]}

Kuhnt, Christian ^{[1
]}

Dietzek, Benjamin ^{[1
,3
]}

Schmitt, Michael ^{[1
]}

Popp, Juergen ^{[1
,3
]}

Schwalbe, Matthias ^{[2
]}

Krieck, Sven ^{[2
]}

Goerls, Helmar ^{[2
]}

Heinemann, Frank W. ^{[4
]}

Rau, Sven ^{[2
,4
]}

机构：

[1] Univ Jena, Inst Phys Chem, D-07742 Jena, Germany

[2] Univ Jena, Inst Inorgan & Analyt Chem, D-07742 Jena, Germany

[3] Inst Photon Technol Jena eV, D-07745 Jena, Germany

[4] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

来源：

DALTON TRANSACTIONS | 2010年 / 39卷 / 09期

关键词：

GAUSSIAN-BASIS SETS; CORRELATED MOLECULAR CALCULATIONS; RESONANCE RAMAN-SPECTROSCOPY; EXTENDED AROMATIC BRIDGES; LIGHT-SWITCH MECHANISM; RUTHENIUM COMPLEXES; RU-II; PHOTOPHYSICAL PROPERTIES; COORDINATION-COMPOUNDS; ELECTRONIC-STRUCTURE;

D O I：

10.1039/b917484b

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of novel regioselective substituted tpphz ligands and two novel mononuclear ruthenium complexes of the type [(tbbpy)(2)Ru(tpphzRn)](PF6)(2) (where tbbpy = 4,4'-di-tert.-butyl-2,2'-bipyridine, tpphz = tetrapyrido[3,2-a:2',3'-c:3 '',2 ''-h:2''',3'''-j]phenazine, with n = 2 and R represents the bromine substituents at different positions) have been synthesized. All compounds were completely characterized by NMR and MS spectroscopy, absorption and steady-state emission spectroscopy as well as emission lifetime and electrochemical measurements. Additionally the solid-state structures of the two isomers [(tbbpy)(2)Ru(Br(2)tpphz)](PF6)(2) 6 and [(tbbpy)(2)Ru(tpphzBr(2))](PF6)(2) 7 are presented and compared with the results of density-functional theory calculations (DFT). Furthermore calculated Raman spectra were obtained by means of DFT calculations and used to assign the vibrational modes of the measured off resonance Raman spectra. A clear influence caused by the electronic effects of the different type and position of the substituents of tpphz on the photophysical behavior was observed.

引用

页码：2359 / 2370

页数：12

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