Optical and electrochemical properties of cyclometalated Rh(III) complexes based on 4,6-diphenylpyrimidine with ethylenediamine, 2,2′-bipyridyl,and 1,10-phenanthroline |
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Authors: | E V Ivanova and K P Balashev |
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Institution: | 1.Herzen State Pedagogical University,St. Petersburg,Russia |
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Abstract: | The Rh(Hdp)2(N∧N)]ClO4 complexes (Hdp− is the monodeprotonated form of 4,6-diphenylpyrimidine and (N∧N) is ethylenediamine, 2,2′-bipyridyl, and 1,10-phenanthroline)
are synthesized and characterized by 1H and 13C NMR, IR, electronic absorption, and emission spectroscopy, as well as by cyclic voltammetry. The magnetic equivalence of
two cyclometalated 4,6-diphenylpyrimidine ligands in the composition of complexes points to the cis position of metalated phenyl rings in the inner sphere. Quasi-reversible one-electron reduction waves are attributed to the
ligand-centered electron transfer to the π* antibonding orbital of heterocyclic ligands, while irreversible oxidation waves
are associated with electron detachment from the Rh-C σ bonding orbital of the {Rh(Hdp)2} metal-complex fragment. The characteristic long-wave-length absorption bands and the vibrationally structured phosphorescence
bands of complexes are assigned to the spin-allowed and spin-forbidden charge-transfer optical transitions between the σRh-C and πHdp* orbitals localized on the {Rh(Hdp)2} fragment of the complex. |
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