Vapochromism and its structural basis in a luminescent Pt(II) terpyridine-nicotinamide complex

A novel Pt(II) terpyridine complex that has a nicotinamide moiety linked to the terpyridyl ligand has been synthesized in good yield and studied structurally and spectroscopically. The complex, [Pt(Nttpy)Cl](PF(6))(2) where Nttpy = 4'-(p-nicotinamide-N-methylphenyl)-2,2':6',2' '-terpyridine, is observed to be brightly luminescent in the solid state at room temperature and at 77 K. The complex exhibits reversible vapochromic behavior and crystallographic change in the presence of several volatile organic solvents. Upon exposure to methanol vapors, the complex changes color from red to orange, and a shift to higher energy is observed in the emission maximum with an increase in excited-state lifetime and emission intensity. The crystal and molecular structures of the orange and red forms, determined by single-crystal X-ray diffraction on the same single crystal, were found to be equivalent in the molecular sense and only modestly different in terms of packing. In both forms, the cationic Pt(II) complexes possess distorted square planar geometries. Analysis of the orange form's crystal packing reveals the presence of solvent molecules in lattice voids, Pt...Pt separations averaging 3.75 A and a zigzag arrangement between nearest neighbor Pt atoms, whereas the red form is devoid of solvent within the crystal lattice and contains complexes stacked with a nearly linear arrangement of Pt(II) ions having an average distance of 3.33 A. On the basis of the crystallographic data, it is evident that sorption of methanol vapor induces a change in intermolecular contacts and Pt...Pt interactions in going from red to orange. Disruption of the d(8)-d(8) metallophilic interactions consequently alters the emitting state from (3)[(d)sigma*-pi*(terpyridine)] that is formally a metal-metal-to-ligand charge transfer (MMLCT) state in the red form to one in which the HOMO corresponds to a more localized Pt(d) orbital in the red form ((3)MLCT).