Issue 9, 2010

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

Abstract

A series of novel regioselective substituted tpphz ligands and two novel mononuclear ruthenium complexes of the type [(tbbpy)2Ru(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)2Ru(Br2tpphz)](PF6)26 and [(tbbpy)2Ru(tpphzBr2)](PF6)27 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.

Graphical abstract: Synthesis and characterization of regioselective substituted tetrapyridophenazine ligands and their Ru(ii) complexes

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2009
Accepted
12 Nov 2009
First published
19 Jan 2010

Dalton Trans., 2010,39, 2359-2370

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

M. Karnahl, S. Tschierlei, C. Kuhnt, B. Dietzek, M. Schmitt, J. Popp, M. Schwalbe, S. Krieck, H. Görls, F. W. Heinemann and S. Rau, Dalton Trans., 2010, 39, 2359 DOI: 10.1039/B917484B

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