Reversible and Stepwise Single-Crystal-to-Single-Crystal Transformation of a Platinum(II) Complex with Vapochromic Luminescence

The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent Pt-II complex bearing an N-heterocyclic carbene [Pt(CN)(2)(tBu-impy)] (tBu-impyH(+) = 1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue (MMLCT)-M-3 emission owing to weak Pt center dot center dot center dot Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the Pt-II complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor.