Reversible Solid-State Phase Transitions between Au-P Complexes Accompanied by Switchable Fluorescence
Reversible Solid-State Phase Transitions between Au-P Complexes Accompanied by Switchable Fluorescence
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伴随可切换荧光的 Au-P 配合物之间的可逆固态相变
DOI：
10.1021/acs.inorgchem.9b03412
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发表时间：
2020-03-02
影响因子：
4.6
通讯作者：
Ren, Zhi-Gang
中科院分区：
文献类型：
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作者：
Jiang, Meng-Sha;Tao, Yan-Hui;Ren, Zhi-Gang
在二氯甲烷中，Au（tht）Cl与3-bdppmapy反应，然后用正己烷浸渍，同时生成六个配合物{（3-bdppmapy）（AuCl）（2）}（n）（1-6; 3-bdppmapy = N，N ′-双（二苯基膦基甲基）-3-氨基吡啶，tht =四氢噻吩）。配合物4-6可以通过挥发溶剂、固相加热或溶剂热反应独立生成。PPh 2-Au-Cl基团向不同方向延伸，形成Au-Au和Au-Au-Au相互作用。配合物4在加热至130 ℃时可转化为5，其中一个Au-Au键断裂，而5在暴露于CH 2Cl 2蒸气中11 h后可回复为4。这种固态相变可以循环使用，并伴随着固态荧光的变化，在五个循环中没有明显的强度衰减。相变和光致发光差异的原因与每个复合物中亲金相互作用的不同数量和强度有关，这可以通过密度泛函理论计算来建模。
Six complexes {(3-bdppmapy)(AuCl)(2)}(n) (1-6; 3-bdppmapy = N,N'-bis(diphenylphosphanylmethyl)-3-aminopyridine and tht = tetrahy-drothiophene) were simultaneously formed by the reaction of Au(tht)CI and 3-bdppmapy in CH2Cl2 followed by infusion with hexane. Complexes 4-6 could be produced independently by volatilizing solvent in air, solid-state heating, or solvothermal reaction. The PPh2-Au-Cl moieties extended in different directions, forming Au-Au and Au-Au-Au interactions. Complex 4 could be converted to 5 by heating to 130 degrees C, with the cleavage of one Au-Au bond, while 5 reverted back to 4 upon exposure to CH2Cl2 vapor over 11 h. This solid-state phase transition could be recycled and was accompanied by a change in solid-state fluorescence, without obvious intensity decay over five cycles. The reason for both the phase transition and difference in photoluminescence is related to the different numbers and strengths of aurophilic interactions in each complex that could be modeled by density functional theory calculations.