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具有膦酸官能化联吡啶配体的发光铂(II)配合物的双向气相变色现象

Two-way vapochromism of a luminescent platinum(ii) complex with phosphonic-acid-functionalized bipyridine ligand.

作者信息

Kobayashi Atsushi, Yamamoto Naotaka, Shigeta Yasuhiro, Yoshida Masaki, Kato Masako

机构信息

Department of Chemistry, Faculty of Science, Hokkaido University, North-10 West-8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.

出版信息

Dalton Trans. 2018 Jan 30;47(5):1548-1556. doi: 10.1039/c7dt04324d.

Abstract

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.

摘要

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。

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