1-D "Platinum Wire" Stacking Structure Built of Platinum(II) Diimine Bis(σ-acetylide) Units with Luminescence in the NIR Region
1-D "Platinum Wire" Stacking Structure Built of Platinum(II) Diimine Bis(σ-acetylide) Units with Luminescence in the NIR Region
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一维 - 铂线 - 由铂 (II) 二亚胺双 (β-乙炔) 单元构建的堆叠结构，在近红外区域发光
DOI：
10.1021/acs.inorgchem.6b01426
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发表时间：
2016-10-17
影响因子：
4.6
通讯作者：
Ni, Jun
中科院分区：
文献类型：
--
作者：
Kang, Jiajia;Zhang, Xiaoxin;Ni, Jun
开发并表征了方形平面铂（II）配合物Pt-（DiBrbpy）（CC 6 H4 Et-4）（2）（1）（DiBrbpy = 4，4-二溴-2，2 '-联吡啶）及其三种溶剂化形式的晶体，即1DMSO、11/2（CH 3CN）和11/8（CH 2Cl 2）。1DMSO和11/2（CH 3CN）含有在可见光范围内发光的准二聚体和二聚体结构，而1.1/8（CH 2Cl 2）由于其固有的一维“铂丝”堆叠结构和强Pt-Pt相互作用而在1022 nm处显示NIR发光。11/8（CH 2Cl 2）表示基于铂（II）二亚胺双（σ-乙炔化物）分子单元的第一化合物，其NIR发光超过1000 nm。1通过改变其颜色和发光性质选择性地响应DMSO和CH 3CN，并且三种溶剂化形式在暴露于相应的溶剂蒸气时可以可逆地相互转化。它们的去溶剂化形式，即分别在加热1DMSO、11/2（CH 3CN）和11/8（CH 2Cl 2）后获得的1a、1b和1c，也可以在暴露于相应的溶剂蒸气时恢复到原始的溶剂化形式。1a和1b分别在998和1018 nm处发射近红外发光峰，表明间接合成方法是实现长波长近红外发光的有力替代方法。相比之下，1c表现出红色发光，具有以667 nm为中心的宽的非结构化发射带。对有机溶剂蒸气和加热的所有响应是由于结构转变，其导致固态中（MLCT）-M-3/（LLCT）-L-3和（MMLCT）-M-3之间的最低能量激发态的转化，如时间依赖密度泛函理论（TD-DFT）计算所支持的。
A square-planar platinum(II) complex, Pt-(DiBrbpy)(C CC6H4Et-4)(2) (1) (DiBrbpy = 4,4-dibromo-2,2'-bipyridine), and crystals of its three solvated forms, namely, 1DMSO, 11/2(CH3CN), and 11/8(CH2Cl2), were developed and characterized. 1DMSO and 11/2(CH3CN) contain quasi-dimeric and dimeric structures with luminescence in the visible range, whereas 1.1/8(CH2Cl2) exhibits NIR luminescence at 1022 nm due to its intrinsic 1-D "platinum wire" stacking structure with strong Pt-Pt interactions. 11/8(CH2Cl2) represents the first compound based on platinum(II) diimine bis(sigma-acetylide) molecular units with the NIR luminescence beyond 1000 nm. 1 selectively responds to DMSO and CH3CN by changing its color and luminescence property and the three solvated forms can be reversibly converted to each other upon exposure to corresponding solvent vapors. Their desolvated forms, namely 1a, 1b, and 1c, obtained after heating 1DMSO, 11/2(CH3CN), and 11/8(CH2Cl2), respectively, can also be restored to the original solvated forms upon exposure to corresponding solvent vapors. 1a and 1b emit NIR luminescence peaked at 998 and 1018 nm respectively, suggesting indirect synthetic methods as powerful alternatives to achieve NIR luminescence with long wavelength. In contrast, 1c exhibits a red luminescence with a broad unstructured emission band centered at 667 nm. All the responses to organic solvent vapors and heating are due to the structural transformations which result in the conversion of the lowest energy excited states between (MLCT)-M-3/(LLCT)-L-3 and (MMLCT)-M-3 in solid-state as supported by time-dependent density functional theory (TD-DFT) calculations.