The diimine-dithiolato ambipolar complexes Pt(dbbpy)(tdt) and Pt(dmecb)(bdt) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine; tdt(2-) = 3,4-toluenedithiolate; dmecb = 4,4'-dimethoxyester-2,2'-bipyridine; bdt(2-) = benzene-1,2-dithiolate) are prepared herein. Pt(dmecb)(bdt) exhibits photoconductivity that remains constant (photocurrent density of 1.6 mA/cm(2) from a 20 nm thin film) across the entire visible region of the solar spectrum in a Schottky diode device structure. Pt(dbbpy)(tdt) acts as donor when combined with the strong nitrofluorenone acceptors 2,7-dinitro-9-fluorenone (DNF), 2,4,7-trinitro-9-fluorenone (TRNF), or 2,4,5,7-tetranitro-9-fluorenone (TENF). Supramolecular charge transfer stacks form and exhibit various donor-acceptor stacking patterns. The crystalline solids are "black absorbers" that exhibit continuous absorptions spanning the entire visible region and significant ultraviolet and near-infrared wavelengths, the latter including long wavelengths that the donor or acceptor molecules alone do not absorb. Absorption spectra reveal the persistence of donor-acceptor interactions in solution, as characterized by low-energy donor/acceptor charge transfer (DACT) bands. Crystal structures show closely packed stacks with distances that underscore intermolecular DACT. (1)H NMR provides further evidence of DACT, as manifested by upfield shifts of aromatic protons in the binary adducts versus their free components, whereas 2D nuclear Overhauser effect spectroscopy (NOESY) spectra suggest coupling between dithiolate donor protons with nitrofluorenone acceptor protons, in correlation with the solid-state stacking. The NMR spectra also show significant peak broadening, indicating some paramagnetism verified by magnetic susceptibility data. Solid-state absorption spectra reveal further red shifts and increased relative intensities of DACT bands for the solid adducts vs solution, suggesting cooperativity of the DACT phenomenon in the solid state, as further substantiated by νC-O and νN-O IR bands and solid-state tight-binding computational analysis.

The organic ligand 4,4 0 -diisopropoxyester-2,2 0 -bipyridine, C 18 H 20 N 2 O 4 (1), crystallizes in the triclinic crystal system P-1 and the molecule occupies a special position in the unit cell. In the crystal, molecules form stacks with partial overlapping of the pyridine rings. The Pt(II) dichloro complex of 1 crystallizes from a mixture of ethanol/hexane and from dichloromethane to form orange and yellow crystals, respectively. The orange non-solvated crystals of the (bipyridine)(dichloro)platinum(II) complex C 18 H 20 N 2 O 4 PtCl 2 (2) crystallize in the triclinic crystal system P-1 as well with two independent molecules in the unit cell. In the crystal packing, molecules form two types of dimers with Pt1ÁÁÁPt1A and Pt2ÁÁÁPt2A distances of 3.478 and 5.186 Å , respectively. The yellow crystals, as a solvated pseudo-polymorph C 18 H 20 N 2 O 4 PtCl 2 Á1.5 CH 2 Cl 2 (3) also crystallize in the triclinic crystal system P-1 with two independent molecules in the unit cell. In the crystal packing, molecules form Pt2ÁÁÁPt1ÁÁÁPt1AÁÁÁPt2A intermolecular contacts with alternating distances 3.501 and 3.431 Å , respectively, forming infinite chains. Graphical Abstract The dichloro(bipyridine)platinum complex, dichloro(4,4 0 -diisopropoxyester-2,2 0 -bipyridine)-platinum(II), forms single crystals as a stable non-solvated form and a solvated polymorph with dramatically different supramolecular structure and short contacts.Keywords X-ray diffraction Á [4,4 0 -diisopropoxyester-2, 2 0 -bi-pyridine] Á [dichloro(4, 4 0 -diisopropoxyester-2, 2 0 -bipyridine)-platinum(II)] Á Supramolecular interactions Á Pseudo-polymorphism

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