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
文摘
Two new complexes [CuI3(L1)I3]n (1, L1 = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole) and [CuI3(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.