Luminescent Cu4I4-Cu3(Pyrazolate)3 Coordination Frameworks: Postsynthetic Ligand Substitution Leads to Network Displacement and Entanglement
Luminescent Cu4I4-Cu3(Pyrazolate)3 Coordination Frameworks: Postsynthetic Ligand Substitution Leads to Network Displacement and Entanglement
复制标题
发光 Cu4I4-Cu3(吡唑)3 配位框架：合成后配体取代导致网络移位和纠缠
DOI：
10.1021/acs.inorgchem.7b02144
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发表时间：
2017
影响因子：
4.6
通讯作者：
Li Dan
中科院分区：
文献类型：
--
作者：
Zhan Shun-Ze;Li Mian;Zheng Ji;Wang Qin-Juan;Ng Seik Weng;Li Dan
Six daughter complexes based on two-dimensional (2-D) luminescent Cu4I4–Cu3Pz3(Pz = pyrazolate) coordination networks, which exhibit an uncommon Cu4I4L3L′ (L = pyridine; L′ = acetonitrile, pyridine, pyrazine, 1,4-diazabicyclo[2.2.2]octane, triphenylphosphine, none) local configuration, were prepared through a postsynthetic modification method starting from a parent complex (L′ = NH3). This work has successfully implemented the single-site substitution of Cu4I4-based coordination frameworks, which have rarely been reported for isolated Cu4I4-type compounds, by taking advantage of the solvent-assisted ligand substitution strategy recently developed in metal–organic framework (MOF) chemistry. Such a procedure not only resulted in the variation of local geometry in the Cu4I4units but also led to interlayer network displacement and entanglement. Particularly, an interesting topological transformation (from 2-D to 2-D → 3-D interpenetration) occurred when linear bidentate linkers (e.g., pyrazine and 1,4-diazabicyclo[2.2.2]octane) are inserted between the 2-D layers. Moreover, the variation in the L′ sites can effectively tune the emission colors, ranging from green to orange (λemmax540–605 nm at room temperature). The photoluminescence origins are tentatively assigned to be a mixture of3MLCT and3XLCT, different from that of the well-studied isolated Cu4I4-type complexes.
