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The synthesis and characterisation of Rh(III) complexes with pyridyl triazole ligands
Authors:Helen M Burke  John F Gallagher  Johannes G Vos
Institution:a National Centre for Sensor Research, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland
b National Institute for Cellular Biology, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland
c Dipartimento di Chimica dell'Universita, Universita di Ferrara, 44100 Ferrara, Italy
Abstract:A series of Rh(III) mixed ligand polypyridine type complexes have been prepared. Complexes of the form Rh(L)2(L)]n+, where n=2/3, L=2,2-bipyridine (bpy)/1,10-phenanthroline (phen) and L=3-(pyridin-2-yl)-1,2,4-triazole (Hpytr), 1-methyl-3-(pyridin-2-yl)-1,2,4-triazole (1M3pytr), 4-methyl-3-(pyridin-2-yl)-1,2,4-triazole (4Mpytr), 3,5-bis(pyridin-2-yl)-1,2,4-triazole (Hbpt), 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (NH2bpt) and 3-(pyridin-2-yl)-5-phenyl-1,2,4-triazole (HPhpytr), have been prepared and their synthesis and characterisation are reported. Crystals of Rh(bpy)2(Phpytr)](PF6)2 and Rh(phen)2(NHbpt)](PF6)2 were obtained and their structures determined. Analysis of X-ray crystallographic data showed that coordination of the metal centre in Rh(phen)2(NHbpt)](PF6)2 occurs via the amine moiety and a nitrogen of the pyridine ring. NMR studies illustrated that coordination to the NH2bpt ligand was also possible via a nitrogen of the triazole ring and the pyridine ring forming the complex Rh(phen)2(NH2bpt)](PF6)3. The absorption and emission properties of the complexes studied were found to be π-π* in nature and preliminary evidence suggests that all complexes with the exception of Rh(phen)2(NHbpt)](PF6)2 and Rh(bpy)2(NHbpt)](PF6)2 are dual emitting at 77 K.
Keywords:Rhodium(III)  Triazole  Crystal structure  Electronic properties  1H NMR
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