Counteranion-Triggered and Excitation-Dependent Chemopalette Effect in a Supramolecular Dual-Emissive System Based on Cu3Pz3
Counteranion-Triggered and Excitation-Dependent Chemopalette Effect in a Supramolecular Dual-Emissive System Based on Cu3Pz3
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基于 Cu(3)Pz(3) 的超分子双发射系统中抗衡阴离子触发和激发相关的化学调色板效应
DOI：
10.1021/acs.inorgchem.8b02203
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发表时间：
--
影响因子：
4.6
通讯作者：
Dan Li
中科院分区：
文献类型：
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作者：
Shun-Ze Zhan;Wei Chen;Weigang Lu;Ji Zheng;Fei Ding;Tong Feng;Dan Li
通过溶剂热反应合成了三种基于Cu 3 Pz 3的同构配合物（Cu 3L 3）2（CuX）2（1-ClO 4，1-NO3，1-Br，其中X分别为ClO 4-，NO3-，Br-）.吡唑基（Pz）高度专一性地形成平面三核Cu_3 Pz_3单元。两个Cu 3L 3单元进一步通过NPy-Cu-NPy（Py = 4-吡啶基）键连接形成八核椅型分子（Cu 3L 3）2（CuX）2，然后通过三聚体间的亲铜性自组装形成链状超聚集体[Cu 3 Pz 3] 2和CuPy 2X.用不同的抗衡阴离子在紫外光照射下，配合物（ClO 4-，NO3-，Br-）可发出从红色到绿色的多种发光，而1-ClO 4和1-NO3只发出低能（LE）橙子光（λemmax= 585 nm）和红色（λemmax= 640 nm）发射，而1-Br表现出兴奋依赖性（260-360 nm）从黄色到绿色的发射，这是由于两种可分辨发射的相对强度的变化，高能量（HE，λemmax= 520 nm）和LE（λemmax= 630 nm）。基于准分子[Cu 3 Pz 3] 2单位，将双发射分配给3CC（LE状态）和基于CuPy 2X单位的3XLCT/3 MLCT（HE状态）。本工作通过调控双发射体系中的抗衡阴离子和激发能实现了化学调色板效应。它提供了宝贵的见解双发射材料的性质，并在这样的系统中的光物理机制的进一步调查。
Three Cu3Pz3-based isostructural complexes (Cu3L3)2(CuX)2(labeled as1-ClO4,1-NO3, and1-Br, where X = ClO4–, NO3–, and Br–, respectively) were prepared by solvothermal reactions of an angular bifunctional pyridyl–pyrazole ligand, 4-(pyridin-4′-ylthio)-3,5-dimethyl-1H-pyrazole (HL), with Cu(ClO4)2, Cu(NO3)2, and CuBr, respectively. Pyrazolate (Pz) groups are highly specific to form planar trinuclear Cu3Pz3units. Two Cu3L3units are further connected by two CuX units through NPy–Cu–NPy(Py = 4-pyridyl) bonds to form an octanuclear chairlike molecule (Cu3L3)2(CuX)2, which then self-assembles through intertrimeric cuprophilicity to construct chainlike supraaggregates featuring two luminophores, [Cu3Pz3]2and CuPy2X. With different counteranions (ClO4–, NO3–, and Br–), the complexes give off various emissions from red to green upon UV irradiation.1-ClO4and1-NO3show only low-energy (LE) orange (λemmax= 585 nm) and red (λemmax= 640 nm) emissions, while1-Br exhibits excitation-dependent (260–360 nm) emissions from yellow to green due to variation in the relative intensities of two resolvable emissions, high energy (HE, λemmax= 520 nm) and LE (λemmax= 630 nm). The dual emissions are assigned to3CC (LE states) based on excimeric [Cu3Pz3]2units and3XLCT/3MLCT (HE states) based on CuPy2X units. This work realizes a chemopalette effect through regulations of the counteranion and excitation energy in a dual-emissive system. It provides valuable insights into the nature of dual-emissive materials and the further investigation of the photophysical mechanism in such a system.