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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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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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Authors and Affiliations

  1. Herzen State Pedagogical University, St. Petersburg, 191186, Russia

    E. V. Ivanova & K. P. Balashev

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  1. E. V. Ivanova
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  2. K. P. Balashev
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Correspondence to K. P. Balashev.

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Original Russian Text © E.V. Ivanova, K.P. Balashev, 2010, published in Optika i Spektroskopiya, 2010, Vol. 108, No. 4, pp. 611–617.

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Ivanova, E.V., Balashev, K.P. Optical and electrochemical properties of cyclometalated Rh(III) complexes based on 4,6-diphenylpyrimidine with ethylenediamine, 2,2′-bipyridyl, and 1,10-phenanthroline. Opt. Spectrosc. 108, 574–580 (2010). https://doi.org/10.1134/S0030400X10040119

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  • DOI: https://doi.org/10.1134/S0030400X10040119

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