Reduced and excited states of (bpym)[PtCl(2)](n)() (bpym = 2,2'-bipyrimidine; n = 1, 2): experiments and DFT calculations |
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Authors: | Kaim Wolfgang Dogan Akbey Wanner Matthias Klein Axel Tiritiris Ioannis Schleid Thomas Stufkens Derk J Snoeck Theo L McInnes Eric J L Fiedler Jan Zális Stanislav |
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Institution: | Institut für Anorganische Chemie, Universit?t Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany. kaim@iac.uni-stuttgart.de |
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Abstract: | The complexes (bpym)PtCl(2) (1) and the new (micro-bpym)PtCl(2)](2) (2), bpym = 2,2'-bipyrimidine, were synthesized and, in the case of 1, crystallized in solvent-free form for X-ray diffraction. The molecules 1 exhibit two different kinds of stacking motifs in the crystal with an interstack CH--N interaction. Complexes 1 and 2 were found to be sufficiently soluble for cyclic voltammetry, spectroscopy (absorption and emission), and spectroelectrochemical studies (UV-vis, EPR). As a result of single or double coordination of the strongly sigma-accepting PtCl(2)] fragment to bpym, the paramagnetic anions 1(*)(-)() and 2(*)(-)() and the dianions 1(2-) and 2(2-) could be reversibly generated, despite the presence of metal-halide bonds. DFT calculations of A((195)Pt) and g tensor components confirm that the singly occupied MOs of the monoanionic species have mainly pi(bpym) character with nonnegligible platinum d orbital participation. The assignments of the electronic absorption and emission and resonance Raman spectra for both complexes are supported by DFT calculations. |
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