TY - JOUR
T1 - Charge-transfer metal-organic frameworks based on CuCN architecture units
T2 - Crystal structures, luminescence properties and theoretical investigations
AU - Huang, Rong Yi
AU - Xue, Chen
AU - Zhu, Chang Hai
AU - Wang, Zhu Qing
AU - Xu, Heng
AU - Ren, Xiao Ming
N1 - Publisher Copyright:
© 2014 The Royal Society of Chemistry.
PY - 2014
Y1 - 2014
N2 - Four CuCN complexes, namely Cu4(CN)4(bix)2 (1), Cu2(CN)2(bmimb) (2), Cu2(CN)2(bmimb) (3) and Cu3(CN)3(bimb) (4), have been prepared via the synchronous redox and self-assembly reaction of Cu(NO3)2, K4[Fe(CN)6] and three structurally related flexible bis(imidazole) ligands, 1,4-bis(imidazol-1-ylmethyl)benzene (bix), 1,4-bis(2-methylimidazol-1-ylmethyl)benzene (bmimb) and 4,4′-bis(1-imidazolyl-1-ylmethyl)biphenyl (bimb) under solvothermal conditions. Although all prepared complexes contain one-dimensional CuCN subchains, they have different structures of 21 helical chain, meso-helical chain, 21-helical chain and zigzag chain for 1, 2, 3 and 4, respectively. Complex 1 presents a three-dimensional framework with (10, 3)-d (utp) topology and exhibits an interesting five-fold interpenetration structure attributed as Class Ia type. Moreover, the five-fold entangled network is turned into an unprecedented three-dimensional binodal (3,6)-connected self-penetrated network via the Cu⋯Cu bond interactions. Most interestingly, 2 and 3 are a pair of isomers, and also generate a three-dimensional uninodal (10, 3) network with ThSi2 and utq topology, respectively, which all display an interesting three-fold interpenetration, and also belong to Class Ia type. Complex 4 displays a distorted two-dimensional (6, 3) topology layer, and further forms a three-dimensional supramolecular structure by weak π⋯π interactions. It is indicated that the organic ligands play a crucial role in the final product structures as well as the solvents. Meanwhile, the complexes present strong green (λmax = 553 (1), 565 (2), 565 (3) and 563 nm (4)) photoluminescence in the solid state at room temperature. The theoretical calculations show that the intense green experimental band can be assigned to a combination of the cyanide group to copper(i) center and cyanide group to cyanide group charge transfer transitions. Additionally, the thermal analyses show that complexes 1-4 possess high thermal stabilities.
AB - Four CuCN complexes, namely Cu4(CN)4(bix)2 (1), Cu2(CN)2(bmimb) (2), Cu2(CN)2(bmimb) (3) and Cu3(CN)3(bimb) (4), have been prepared via the synchronous redox and self-assembly reaction of Cu(NO3)2, K4[Fe(CN)6] and three structurally related flexible bis(imidazole) ligands, 1,4-bis(imidazol-1-ylmethyl)benzene (bix), 1,4-bis(2-methylimidazol-1-ylmethyl)benzene (bmimb) and 4,4′-bis(1-imidazolyl-1-ylmethyl)biphenyl (bimb) under solvothermal conditions. Although all prepared complexes contain one-dimensional CuCN subchains, they have different structures of 21 helical chain, meso-helical chain, 21-helical chain and zigzag chain for 1, 2, 3 and 4, respectively. Complex 1 presents a three-dimensional framework with (10, 3)-d (utp) topology and exhibits an interesting five-fold interpenetration structure attributed as Class Ia type. Moreover, the five-fold entangled network is turned into an unprecedented three-dimensional binodal (3,6)-connected self-penetrated network via the Cu⋯Cu bond interactions. Most interestingly, 2 and 3 are a pair of isomers, and also generate a three-dimensional uninodal (10, 3) network with ThSi2 and utq topology, respectively, which all display an interesting three-fold interpenetration, and also belong to Class Ia type. Complex 4 displays a distorted two-dimensional (6, 3) topology layer, and further forms a three-dimensional supramolecular structure by weak π⋯π interactions. It is indicated that the organic ligands play a crucial role in the final product structures as well as the solvents. Meanwhile, the complexes present strong green (λmax = 553 (1), 565 (2), 565 (3) and 563 nm (4)) photoluminescence in the solid state at room temperature. The theoretical calculations show that the intense green experimental band can be assigned to a combination of the cyanide group to copper(i) center and cyanide group to cyanide group charge transfer transitions. Additionally, the thermal analyses show that complexes 1-4 possess high thermal stabilities.
UR - http://www.scopus.com/inward/record.url?scp=84912059604&partnerID=8YFLogxK
U2 - 10.1039/c4ra11652f
DO - 10.1039/c4ra11652f
M3 - 文章
AN - SCOPUS:84912059604
SN - 2046-2069
VL - 4
SP - 61200
EP - 61209
JO - RSC Advances
JF - RSC Advances
IS - 105
ER -