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Syntheses, Characterization, X‐ray Crystal Structure, Redox and Photophysical Properties of Polypyridylruthenium(II) Complexes Containing Carboxylate‐Substituted Pyridyltriazoles
Author(s) -
Mehmetaj Bedri,
Haasnoot Jaap G.,
De Cola Luisa,
van Albada Gerard A.,
Mutikainen Ilpo,
Turpeinen Urho,
Reedijk Jan
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200207)2002:7<1765::aid-ejic1765>3.0.co;2-#
Subject(s) - chemistry , carboxylate , redox , characterization (materials science) , crystal structure , crystallography , x ray crystallography , x ray , photochemistry , stereochemistry , inorganic chemistry , nanotechnology , diffraction , materials science , physics , quantum mechanics , optics
The syntheses and properties of two novel [Ru(bpy) 2 (L−L′)] n + complexes with L−L′ = 3‐carboxy‐5‐(pyrid‐2′‐yl)‐1,2,4triazole ( H 2 cpt ) or 3‐(ethoxycarbonyl)‐5‐(pyrid‐2′‐yl)‐1,2,4‐triazole ( Hcept ) ligands are described. Previous publications on Ru II complexes containing (pyrid‐2′‐yl)‐1,2,4‐triazoles revealed that their coordination is possible via N1 and N4 of the triazole ring. 1 H NMR spectroscopic data and the crystal structure of [Ru(bpy) 2 (cept)]PF 6 ·H 2 O ( 2 ) indicate that the coordination of the Hcpt − and cept − occurs via N1 of the triazole ring. The crystals of 2 are monoclinic and belong to the space group P 2 1 / n with a = 12.339(7), b = 16.512(7), c = 16.802(8) Å, β = 110.29(4)°, and Z = 4. A water molecule is hydrogen‐bonded to the carbonyl oxygen atom of the ethoxycarbonyl group with an O ··· O distance of 2.891 Å. Spectroscopic measurements reveal that H 2 cpt and Hcept are strong σ‐donor ligands. When coordinated to a ruthenium(II) centre, both triazole ligands reported in this study lost their acidic triazole hydrogen atoms and became negatively charged, resulting in even stronger σ‐donor ligands, as demonstrated by a negative shift of their redox potentials compared to the complexes containing the neutral ligand. The complexes reported in this study showed 3 MLCT‐based luminescence emission, both at room temperature and at 77 K. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)