STRUCTURE, OPTICAL AND ELECTROCHEMICAL PROPERTIES OF BINUCLEAR COMPLEXES WITH PLATINATED 2-PHENYLBENZOTHIAZOL AND BRIDGING 2-MERCAPTO-DERIVATIVES OF PYRIDINE, PYRIMIDINE, BENZOTHIAZOLE, AND BENZOXAZOLE
E. A. Katlenok1, A. A. Zolotarev2, A. Yu. Ivanov2, S. N. Smirnov2, K. P. Balashev1
1Gertsen Russian State Pedagogical University, St. Petersburg, Russia
2St. Petersburg State University, St. Petersburg, Russia
Keywords: биядерные циклометаллированные комплексы Pt(II), РСА, ЯМР
Н,
Pt спектроскопия
, электронная спектроскопия поглощения и испускания, вольтамперометрия окисления и восстановления, binuclear cyclometalated complexes of Pt(II), X-ray crystallography,
Н
,
Pt NMR spectroscopy
, electronic absorption and emission spectroscopy, redox voltammetry
Abstract
Binuclear [Pt(bt)m-(N^S)]
2 complexes (bt
- is the deprotonated form of 2-phenylbenzothiazole, (N^S)
- = 2-mercaptopyridineate, 2-mercaptopyrimidineate, 2-mercaptobenzothiazoleate, 2-mercaptobenzoxazoleate ions) are characterized by the following methods: X-ray crystallography,
1Н and
195Pt NMR spectroscopy, electronic absorption and emission spectroscopy, cyclic voltammetry. The occurrence of the Pt-Pt chemical bond and complexes in both crystalline state and solution in the form of cis -N
(bt),S-binding isomers with the asymmetrical arrangement of two cyclometalated and two bridging ligands is shown. Long-wavе absorption bands and luminescence of the complexes in the red spectral range are due to spin-allowed and spin-forbidden optical charge transfer transitions from the metal-metal bond to the metalated ligand. In cyclic voltammetry, two-electron redox waves of the complexes are attributed to metal- and ligand-centered processes involving s* HOMO and p*(bt) LUMO of the complexes.
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