Abstract
The effect of heterocyclic metalated and bridging ligands on the optical and electrochemical properties of [Pt(C^N)(μ-N^S)]2 complexes ((C^N)− and (N^S)− are the deprotonated forms of 1-phenylpyrazole, 2-tolylpyridine, benzo[h]quinoline, 2-phenylbenzothiazole and 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyridine) is studied by 1H NMR, electronic absorption, and emission spectroscopy, as well as by voltammetry. The long-wavelength spin-allowed (415–540 nm) absorption bands of the complexes are attributed to the metal-metal-to-ligand charge transfer (MMLCT) optical transitions. It is shown that the interaction of the d Z2 and π *)(C^N orbitals of two {Pt(C^N)} fragments of binuclear complexes leads to a cathodic shift (0.5–1.0 V) of their metal-centered oxidation potential and to an anodic shift (0.1–0.2 V) of their ligand-centered reduction potential with respect to [Pt(C^N)En]+ complexes. The luminescence of binuclear complexes in solutions at room temperature is assigned to the spin-forbidden MMLCT transition. It is shown that, in frozen (77 K) solutions, in addition to the MMLCT optical transitions, spin-forbidden radiative processes occur from the intraligand (π(C^N)−π *(C^N) ) and metal-to-ligand charge transfer (dPt−π *(C^N) ) excited states.
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Original Russian Text © E.A. Katlenok, K.P. Balashev, 2014, published in Optika i Spektroskopiya, 2014, Vol. 117, No. 3, pp. 389–395.
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Katlenok, E.A., Balashev, K.P. The effect of the nature of peripheral platinated and bridging mercapto ligands on the optical and electrochemical properties of binuclear Pt(II) complexes with a metal-metal chemical bond. Opt. Spectrosc. 117, 374–380 (2014). https://doi.org/10.1134/S0030400X14090094
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DOI: https://doi.org/10.1134/S0030400X14090094