A square-planar platinum(II) complex, Pt(DiBrbpy)(C≡CCHEt-4) (1) (DiBrbpy = 4,4-dibromo-2,2'-bipyridine), and crystals of its three solvated forms, namely, 1·DMSO, 1·1/2(CHCN), and 1·1/8(CHCl), were developed and characterized. 1·DMSO and 1·1/2(CHCN) contain quasi-dimeric and dimeric structures with luminescence in the visible range, whereas 1·1/8(CHCl) exhibits NIR luminescence at 1022 nm due to its intrinsic 1-D "platinum wire" stacking structure with strong Pt-Pt interactions. 1·1/8(CHCl) represents the first compound based on platinum(II) diimine bis(σ-acetylide) molecular units with the NIR luminescence beyond 1000 nm. 1 selectively responds to DMSO and CHCN by changing its color and luminescence property and the three solvated forms can be reversibly converted to each other upon exposure to corresponding solvent vapors. Their desolvated forms, namely 1a, 1b, and 1c, obtained after heating 1·DMSO, 1·1/2(CHCN), and 1·1/8(CHCl), respectively, can also be restored to the original solvated forms upon exposure to corresponding solvent vapors. 1a and 1b emit NIR luminescence peaked at 998 and 1018 nm respectively, suggesting indirect synthetic methods as powerful alternatives to achieve NIR luminescence with long wavelength. In contrast, 1c exhibits a red luminescence with a broad unstructured emission band centered at 667 nm. All the responses to organic solvent vapors and heating are due to the structural transformations which result in the conversion of the lowest energy excited states between MLCT/LLCT and MMLCT in solid-state as supported by time-dependent density functional theory (TD-DFT) calculations.

A concurrent, selective, naked-eye perceivable, sensitive, reversible, reproducible, and easy to use sensor for detecting vapors of benzene compounds has been developed.

Abstract.A platinum(II) complex Pt(DiBrbpy)Cl 2 (1) based on 4,4Ј-dibromo-2,2Ј-bipyridine ligand was synthesized and characterized. Interestingly, two solvated phases of 1 with different amounts of crystalline CH 2 Cl 2 molecules, 1·1/3(CH 2 Cl 2 ) (yellow) and 1·3/2(CH 2 Cl 2 ) (red), were obtained. In the solid state, 1·1/3(CH 2 Cl 2 ) exhibits a 3D supramolecular structure based on Pt(DiBrbpy)Cl 2 monomer and emits a weak yellow luminescence at 541 nm (579, sh).

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