Chromism of Tartrate-Bridged Clamshell-like Platinum(II) Complex: Intramolecular Pt Pt Interaction-Induced Luminescence Vapochromism and Intermolecular Interactions-Triggered Thermochromism
Chromism of Tartrate-Bridged Clamshell-like Platinum(II) Complex: Intramolecular Pt Pt Interaction-Induced Luminescence Vapochromism and Intermolecular Interactions-Triggered Thermochromism
复制标题
DOI：
10.1021/acs.inorgchem.8b02074
复制
发表时间：
2018-11-19
影响因子：
4.6
通讯作者：
Fujihara, Takashi
中科院分区：
文献类型：
--
作者：
Ohno, Keiji;Kusano, Yukiko;Fujihara, Takashi
合成了一种新型的外消旋酒石酸合铂（II）的蛤壳状发光配合物：rac-[{Pt-II（4 Me（2）bpy）（2）（mu-tart）]（Pt-2;（4）Me（2）bpy：4，4 '-二甲基-2，2'-联吡啶; tartH（2）（2-）：酒石酸盐），并研究了其汽相、热相和溶剂化变色行为。该配合物被分离成四种晶体形式，即Pt-2.4H（2）O（在环境光下的颜色：黄色，λ（em）= 573 nm，分子内Pt Pt分离：3.55 A），Pt-2.4H（2）O（在环境光下的颜色：黄色，λ（em）= 573 nm，分子内Pt Pt分离：3.55 A），Pt-2.4H（2）O（在环境光下的颜色：黄色，λ（em）= 573 A），Pt-2.4H（2）O（在环境光下的颜色：黄色，λ（em）= 573 A），Pt-2.4H（2）O（在环境光下的颜色：黄色，λ（em）= 573 A），Pt-2.4H（2）O（在环境光下的颜色：黄色，λ（em）= 573 A）。4 MeOH（红色，650 nm，3.33埃）、无水Pt-2（红色，无发光，3.70 A）和Pt-2.2H（2）O（橙子，595 nm，3.60 A）。通过时间和/或温度依赖性粉末X-射线衍射观察到蒸气和热响应性晶体-晶体相变，并且通过单晶X-射线晶体学或粉末X-射线衍射的Rietveld精修确定上述晶型的分子和晶体结构。甲醇在Pt-2.4H（2）O中的气相扩散引起了Pt-2.4MeOH的可逆相变。这种结构转变显着改变了分子内的Pt-Pt相互作用，影响吸收和发射颜色。因此，发光色性源于Pt-2.4H（2）O的三重态金属配体-配体电荷转移态（（3）（MLtart）LbpyCT）和Pt-2- 4 MeOH的三重态金属-金属-配体电荷转移态（3 MML CT）之间发光性质的交替。Pt-2.4H（2）O在高温下发生相变，生成无水Pt-2，在常压下，无水Pt-2自发转变为Pt-2.2H（2）O。H_2O向Pt-2.2H（2）O的气相扩散导致了Pt-2.4H（2）O的重构。热色性源于堆叠复合物之间的分子间相互作用的变化。采用Kamlet塔夫脱溶致变色方程、受体数和溶剂的ET（30）标度评价了溶致变色性，溶剂的氢键酸性对溶剂依赖性吸收性质有显著贡献。
A novel luminescent clamshell-like platinum(II) complex with rac-tartrate, rac-[{Pt-II(4Me(2)bpy)(2)(mu-tart)] (Pt-2; (4)Me(2)bpy: 4,4'-dimethyl-2,2'-bipyridine; tartH(2)(2-): tartrate), was synthesized, and its vapo-, thermo-, and solvatochromic behavior was studied. The complex was isolated in four crystal forms, namely, Pt-2.4H(2)O (color under ambient light: yellow, lambda(em) = 573 nm, intramolecular Pt Pt separation: 3.55 A), Pt-2. 4MeOH (red, 650 nm, 3.33 angstrom), anhydrate Pt-2 (red, no luminescence, 3.70 A), and Pt-2.2H(2)O (orange, 595 nm, 3.60 A). Vapo- and heat-responsive crystal-to-crystal phase transitions were observed by time- and/or temperature-dependent powder X-ray diffraction, and the molecular and crystal structures of the above crystal forms were determined by either single-crystal X-ray crystallography or Rietveld refinement of powder X-ray diffraction. Vapor diffusion of MeOH to Pt-2.4H(2)O induced a reversible phase transition to Pt-2.4MeOH. This structural transformation significantly changed the intramolecular Pt Pt interactions, affecting the absorption and emission colors. Accordingly, the luminescence chromism originates from alternation of the luminescent nature between a triplet metalligand-to-ligand charge-transfer state ((3)(MLtart)LbpyCT) of Pt-2.4H(2)O and a triplet metal-metal-to-ligand charge-transfer state (3MML CT) of Pt-2-4MeOH. Heating Pt-2.4H(2)O induced a phase transition to anhydrate Pt-2, and under atmospheric conditions, anhydrate Pt-2 transformed spontaneously to Pt-2.2H(2)O. Vapor diffusion of H2O to Pt-2.2H(2)O caused reconstruction of Pt-2.4H(2)O. The thermochromism originates from changes in the intermolecular interactions between stacked complexes. The solvatochromism was evaluated using the Kamlet Taft solvatochromic equation, the acceptor number, and the ET(30) scale for the solvent, and the hydrogen-bond acidity of the solvent contributed significantly to the solvent-dependent absorption properties.