Synthesis and characterization of Pt(CN-p-(C(2)H(5))C(6)H(4))(2)(CN)(2), a crystalline vapoluminescent compound that detects vapor-phase aromatic hydrocarbons.

Abstract

The vapochromic and vapoluminescent compound Pt(CN-p-(C(2)H(5))C(6)H(4))(2)(CN)(2) (abbreviated PtC(2)) is conveniently synthesized by the thermal rearrangement of [Pt(CN-p-(C(2)H(5))C(6)H(4))(4)][Pt(CN)(4)]. Recrystallization of PtC(2) gives a crystalline orange morph (O-PtC(2)) and an amorphous purple morph (P-PtC(2)) that both contain the cis isomer and differ only in their solid-state packing arrangements. Both compounds were fully characterized by elemental analysis, X-ray powder diffraction, NMR, IR, and TGA. O-PtC(2) is vapochromic and vapoluminescent: it reversibly sorbs aromatic hydrocarbons and ethanol from air or nitrogen with resulting color changes and shifts in the emission spectrum. The lambda(max) values (nm) for emission from O-PtC(2) x (guest) are as follows: no guest, 611; toluene, 565; benzene, 586; chlorobenzene, 592; p-xylene, 585; mesitylene, 565; ethanol, 587. In the case of toluene and mesitylene, intermediate emitting phases are observed. Recrystallization of O-PtC(2) from dichloromethane/toluene gave single crystals of PtC(2) x 0.5(toluene). The single-crystal X-ray structure of PtC(2) x 0.5(toluene) contains infinite stacks of cis geometry and planar molecules with chains of platinum atoms parallel to the c axis of the monoclinic unit cell. The average Pt-Pt separation in PtC(2) x 0.5(toluene) is c/4 = 3.288(2) A. There are solvent channels parallel with the c axis that contain the toluene molecule guests. Thin films of O-PtC(2) rapidly sorb toluene from the gas phase to form PtC(2) x 0.25(toluene) and PtC(2) x 0.5(toluene). Long-term exposure gives PtC(2) x 1.0(toluene). Removal of the toluene source causes rapid desorption to PtC(2) x 0.5(toluene) and then to PtC(2) x 0.25(toluene). The remaining 0.25(toluene) lattice guests require heating for rapid removal. X-ray powder diffraction identified the PtC(2),PtC(2) x .25(toluene), and PtC(2) x 0.5(toluene) phases and showed that the sorption of toluene is accompanied by small changes in the unit cell dimensions that include lengthening the Pt-Pt distances in the structure. The sorption process improves the packing in the structure by utilizing some of the free volume for the toluene lattice guests.