PH-Controlled Construction of Cu(I) Coordination Polymers: In Situ Transformation of Ligand, Network Topologies, and Luminescence and UV鈥搗is-NIR Absorption Properties

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• 作者：Zhen-Lan Fang ; Jian-Gang He ; Qi-Sheng Zhang ; Qi-Kai Zhang ; Xiao-Yuan Wu ; Rong-Min Yu ; Can-Zhong Lu
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：November 21, 2011
• 年：2011
• 卷：50
• 期：22
• 页码：11403-11411
• 全文大小：1237K
• 年卷期：v.50,no.22(November 21, 2011)
• ISSN：1520-510X

文摘

Two new complexes [Cu^I₃(L1)I₃]_n (1, L1 = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole) and [Cu^I₃(L2)I₂]_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路5²路6²路7)(5⁴路8²)(4³路5路6⁶). 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鈥搗is-NIR spectrum range. The emissive excited states of 1 and the charge transitions of the optical absorption for 2 are solved by DFT calculations.