%0 Journal Article %1 Kaim.2002 %A Kaim, Wolfgang %A Dogan, Akbey %A Wanner, Matthias %A Klein, Axel %A Tiritiris, Ioannis %A Schleid, Thomas %A Stufkens, Derk J. %A Snoeck, Theo L. %A McInnes, Eric J. L. %A Fiedler, Jan %A Zalis, Stanislav. %D 2002 %J Inorganic Chemistry %K bipyrimidine calcd complex complex;electronic complex;luminescence complex;mol complex;platinum crystal electrochem platinum prepn redn;Raman structure %N 16 %P 4139--4148 %R 10.1021/ic020158f %T Reduced and Excited States of (bpym)PtCl2n (bpym = 2,2'-Bipyrimidine; n = 1, 2): Experiments and DFT Calculations %V 41 %X The complexes (bpym)PtCl2 (1) and the new (m-bpym)PtCl22 (2), bpym = 2,2'-bipyrimidine, were synthesized and, in the case of 1, crystd. in solvent-free form for x-ray diffraction. The mols. 1 exhibit two different kinds of stacking motifs in the crystal with an interstack CH--N interaction. Complexes 1 and 2 are sufficiently sol. for cyclic voltammetry, spectroscopy (absorption and emission), and spectroelectrochem. studies (UV-visible, EPR). As a result of single or double coordination of the strongly s-accepting PtCl2 fragment to bpym, the paramagnetic anions 1.bul.- and 2.bul.- and the dianions 12- and 22- could be reversibly generated, despite the presence of metal-halide bonds. DFT calcns. of A(195Pt) and g tensor components confirm that the singly occupied MOs of the monoanionic species have mainly p (bpym) character with nonnegligible Pt d orbital participation. The assignments of the electronic absorption and emission and resonance Raman spectra for both complexes are supported by DFT calcns. on SciFinder(R)

@article{Kaim.2002, abstract = {The complexes (bpym)PtCl2 (1) and the new (\textgreek{m}-bpym)[PtCl2]2 (2), bpym = 2,2'-bipyrimidine, were synthesized and, in the case of 1, crystd. in solvent-free form for x-ray diffraction. The mols. 1 exhibit two different kinds of stacking motifs in the crystal with an interstack CH--N interaction. Complexes 1 and 2 are sufficiently sol. for cyclic voltammetry, spectroscopy (absorption and emission), and spectroelectrochem. studies (UV-visible, EPR). As a result of single or double coordination of the strongly \textgreek{s}-accepting [PtCl2] fragment to bpym, the paramagnetic anions 1.bul.- and 2.bul.- and the dianions 12- and 22- could be reversibly generated, despite the presence of metal-halide bonds. DFT calcns. of A(195Pt) and g tensor components confirm that the singly occupied MOs of the monoanionic species have mainly \textgreek{p} (bpym) character with nonnegligible Pt d orbital participation. The assignments of the electronic absorption and emission and resonance Raman spectra for both complexes are supported by DFT calcns. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Kaim, Wolfgang and Dogan, Akbey and Wanner, Matthias and Klein, Axel and Tiritiris, Ioannis and Schleid, Thomas and Stufkens, Derk J. and Snoeck, Theo L. and McInnes, Eric J. L. and Fiedler, Jan and Zalis, Stanislav.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2a7ad4755b82c0608865b1818a06e5d1a/huebleriac}, doi = {10.1021/ic020158f}, interhash = {82d77e7d25d3f31b005af26db046e1a3}, intrahash = {a7ad4755b82c0608865b1818a06e5d1a}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {bipyrimidine calcd complex complex;electronic complex;luminescence complex;mol complex;platinum crystal electrochem platinum prepn redn;Raman structure}, number = 16, pages = {4139--4148}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Reduced and Excited States of (bpym)[PtCl2]n (bpym = 2,2'-Bipyrimidine; n = 1, 2): Experiments and DFT Calculations}, volume = 41, year = 2002 }