Kobayashi Atsushi, Yamamoto Naotaka, Shigeta Yasuhiro, Yoshida Masaki, Kato Masako
Department of Chemistry, Faculty of Science, Hokkaido University, North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
Dalton Trans. 2018 Jan 30;47(5):1548-1556. doi: 10.1039/c7dt04324d.
A luminescent Pt(ii) complex [Pt(CN)(Hdpbpy)] (1P; Hdpbpy = 2,2'-bipyridine-4,4'-diphosphonic acid) bearing a phosphonic-acid-functionalized bipyridine ligand was successfully synthesized and its unique two-way vapochromic behaviour investigated. X-ray structure analyses of both the anhydrous 1P and penta-hydrated 1P·5H2O phases clearly reveal the activation of intermolecular PtPt interactions through the adsorption of water vapour. Emission spectroscopy reveals that the penta-hydrated 1P·5H2O complex exhibits an orange emission at 585 nm that shifts in two directions, to a blue-green emission at 469 nm by drying at 100 °C or to a red emission at 701 nm by drying under vacuum at room temperature. Thermogravimetric analyses and powder X-ray diffraction studies clearly reveal that anhydrous 1P, with negligible intermolecular PtPt interactions, is formed by drying at 100 °C whereas the monohydrate 1P·H2O phase, with effective PtPt interactions, is formed by drying under vacuum.
成功合成了一种带有膦酸官能化联吡啶配体的发光铂（II）配合物[Pt(CN)(Hdpbpy)]（1P；Hdpbpy = 2,2'-联吡啶-4,4'-二膦酸），并研究了其独特的双向气致变色行为。无水1P和五水合1P·5H₂O相的X射线结构分析清楚地表明，通过水蒸气吸附激活了分子间的Pt-Pt相互作用。发射光谱表明，五水合1P·5H₂O配合物在585 nm处呈现橙色发射，该发射在两个方向上发生移动，在100°C下干燥时变为469 nm处的蓝绿色发射，或在室温下真空干燥时变为701 nm处的红色发射。热重分析和粉末X射线衍射研究清楚地表明，通过在100°C下干燥形成了分子间Pt-Pt相互作用可忽略不计的无水1P，而通过真空干燥形成了具有有效Pt-Pt相互作用的一水合物1P·H₂O相。
