Luminescent chloride and hexaflurophosphate salts of Pt(Me2bzimpy)Cl+ (Me2bzimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine) are reported. As solids, both compounds are vapochromic, undergoing pronounced and reversible changes of color and emission in the presence of volatile organic compounds. The chloride salt responds to vapors of methanol, chloroform, ethanol, and acetonitrile, undergoing a distinct change in color from yellow to red within seconds. The PF6- salt responded selectively to acetonitrile vapor, changing from yellow to violet while sorbing 1.0 +/- 0.1 equiv. For either salt, leaving vapor-exposed samples in air for several days or heating for several minutes restored the original color. UV-visible absorption spectra and solid-state room temperature and 77 K emission spectra are reported, and the accumulated data are consistent with a decrease in Pt...Pt separation accompanying vapor sorption.

Square-planar cations of the orange form of [Pt(Me2bzimpy)Cl](PF6) x DMF [Me2bzimpy = 2,6-bis(N-methylbenzimidazol-2-yl)pyridine] stack along the b axis in a head-to-tail arrangement with short interplanar spacings (3.35 and 3.39 A). Long intermolecular Pt...Pt contacts [4.336(2) and 4.565(2) A] and comparatively short Me2bzimpy...Me2bzimpy distances are consistent with spectroscopic measurements for orange salts of Pt(Me2bzimpy)Cl+. The DMF solvent molecules line channels parallel to c, which may provide a conduit for vapor absorption. The crystals are vapochromic, changing from orange to violet upon exposure to acetonitrile vapor. The changes in spectroscopic properties accompanying vapor absorption are consistent with changes in intermolecular interactions between complexes.

The direct ion exchange of chloro(2,6-bis(N-methylbenzimidazol-2-yl)pyridine)platinum(II) ([Pt(Me(2)bzimpy)Cl]+) and chloro(2,2':6',2' '-terpyridine)platinum(II) ([Pt(tpy)Cl]+) complexes within a zirconium phosphate (ZrP) framework has been accomplished. The physical and spectroscopic properties of [Pt(Me(2)bzimpy)Cl]+ and [Pt(tpy)Cl]+ intercalated in ZrP were investigated by X-ray powder diffraction and X-ray photoelectron, infrared, absorption, and luminescence spectroscopies. In contrast to unintercalated complexes in fluid solution, which do not emit at room temperature, both intercalated materials in the solid state and in colloidal suspensions exhibit intense emissions at room temperature. A [Pt(Me(2)bzimpy)Cl]+-exchanged ZrP colloidal methanol suspension gives rise to an emission at 612 nm that originates from a lowest (3)MMLCT[dsigma*(Pt) --> pi*(tpy)] state (MMLCT = metal-metal-to-ligand charge transfer) characteristic of strong Pt...Pt interactions. A [Pt(tpy)Cl]+-exchanged ZrP colloidal aqueous suspension exhibits a strong emission band at 600 nm. The accumulated data demonstrate that at high concentrations, [Pt(Me(2)bzimpy)Cl]+ and [Pt(tpy)Cl]+ ions can serve as luminescent pillars inside the ZrP framework.