Department of Chemistry and Research Institute for Biomedical and Advanced Materials, Shantou University, Guangdong 515063, PR China.
Chemistry. 2013 Jul 29;19(31):10217-25. doi: 10.1002/chem.201204632. Epub 2013 Jun 18.
Two classical copper(I)-cluster-based luminophores, namely, Cu4I4 and [Cu3Pz3]2 (Pz = pyrazolate), are immobilized in a supramolecular system through the formation of metal-organic framework (MOF) materials. This series of luminescent MOF materials, namely, [Cu4I4(NH3)Cu3(L1)3]n, [Cu4I4(NH2CH3)Cu3(L1)3]n, and [Cu4I4Cu3(L2)3]n (L1 = 3-(4-pyridyl)-5-(p-tolyl)pyrazolate; L2 = 3-(4-pyridyl)-5-(2,4-dimethylphenyl)pyrazolate), exhibit diverse thermochromism attributed to the relative functioning efficacy of the two coordination luminophores. Such an intriguing chemopalette effect is regulated by the different supramolecular microenvironments between the two-dimensional layers of these MOFs, and in particular, by the fine-tuned Cu-Cu distances in the excimeric [Cu3Pz3]2 luminophore. The structure-property elucidation of the thermochromic behavior allows one to understand these optical materials with unusual dual-emissive properties.
两种经典的基于铜（I）簇的发光体，即 Cu4I4 和 [Cu3Pz3]2（Pz = 吡唑），通过形成金属-有机骨架（MOF）材料固定在超分子系统中。这一系列发光 MOF 材料，即 [Cu4I4(NH3)Cu3(L1)3]n、[Cu4I4(NH2CH3)Cu3(L1)3]n 和 [Cu4I4Cu3(L2)3]n（L1 = 3-(4-吡啶基）-5-(对甲苯基)吡唑；L2 = 3-(4-吡啶基）-5-(2,4-二甲基苯基)吡唑），表现出不同的热致变色性，这归因于两种配位发光体的相对作用效果。这种有趣的化学调色效果受这些 MOFs 的二维层之间不同的超分子微环境调控，特别是受激基 [Cu3Pz3]2 发光体中精细调节的 Cu-Cu 距离调控。对热致变色行为的结构-性质阐明允许人们理解这些具有不寻常双重发射性质的光学材料。
