PH-controlled construction of Cu(I) coordination polymers: in situ transformation of ligand, network topologies, and luminescence and UV-vis-NIR absorption properties.
PH-controlled construction of Cu(I) coordination polymers: in situ transformation of ligand, network topologies, and luminescence and UV-vis-NIR absorption properties.
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DOI：
10.1021/ic2011666
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发表时间：
2011-10
影响因子：
4.6
通讯作者：
Zhen Fang;Jiangang He;Qishn Zhang;Qikai Zhang;Xiaoyuan Wu;R. Yu;Canzhong Lu
中科院分区：
文献类型：
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作者：
Zhen Fang;Jiangang He;Qishn Zhang;Qikai Zhang;Xiaoyuan Wu;R. Yu;Canzhong Lu
用氨水调节CuI与L1反应的pH值，得到了两个新的配合物[Cu(I)(3)(L1)I(3)](N)(1，L1=2，5-双(4-吡啶)-1，3，4-恶二唑)和[Cu(I)(3)(L2)I(2)](N)(2，L2=2，5-双(4-吡啶)-1，2，4-三氮唑)。有趣的是，当反应的pH值增加时，L1的环变化在原位生成了L2。1展示了二维层，而2展示了一种新的3节点4，4，5连通网络拓扑的前所未有的点(Schlafli)：(4·5(2)·6(2)·7)(5(4)·8(2))(4(3)·5·6(6))。虽然1和2都是由CuI和相似的配体构成的，但CuI链和配体的不同排列赋予了它们不同的物理性质。1显示出很强的纯红发光，而2是不发光的，并显示出覆盖整个UV-VIS-NIR光谱范围的宽吸收带。用密度泛函理论计算了1的发射激发态和2的光吸收的电荷跃迁。
Two new complexes [Cu(I)(3)(L1)I(3)](n) (1, L1 = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole) and [Cu(I)(3)(L2)I(2)](n) (2, L2 = 2,5-bis(4-pyridyl)-1,2,4-triazolate) are controllably formed by using aqueous ammonia to regulate the pH value of the reaction involving CuI and L1. Interestingly, L2 of 2 is in situ generated from the ring transform of L1 when increase the pH value of the reaction. 1 exhibits 2-D layer, while 2 shows 3-D MOFs with a novel 3-nodal 4,4,5-connected net topology of an unprecedented Point (Schlafli) symbol: (4·5(2)·6(2)·7)(5(4)·8(2))(4(3)·5·6(6)). Although both 1 and 2 are built of CuI and similar ligands, different arrangements of CuI chains and ligands endow them with different physical properties. 1 displays a strong pure red luminescence emission, while 2 is nonluminescent and shows a broad absorption band covering the whole UV-vis-NIR spectrum range. The emissive excited states of 1 and the charge transitions of the optical absorption for 2 are solved by DFT calculations.