TY - JOUR
T1 - Structures and magnetic properties of copper(ii) and manganese(ii) polymers derived from pseudohalides and a flexible zwitterionic dicarboxylate ligand
AU - Wang, Kun
AU - Yi, Xiu Chun
AU - Wang, Xuan
AU - Li, Xiu Bing
AU - Gao, En Qing
PY - 2013/6/28
Y1 - 2013/6/28
N2 - The flexible zwitterionic dicarboxylate ligand 1,4-bis(4-carboxylato-1- pyridinium)butane (bcpb) assumes different conformations to collaborate with pseudohalides in various coordination modes to produce coordination polymers in which distinct anionic motifs with mixed carboxylate and pseudohalide bridges are interlinked by the cationic butylenebis(pyridinium) tethers. The Cu(ii) compound, [Cu2(bcpb)(N3)4]n·nH 2O (1), is a 1D coordination polymer based on the defective dicubane-like [Cu4(μ3-1,1,1-N3) 2(μ-1,1-N3)2(μ-1,1-OCO)2] cluster. With Mn(ii), four distinct 3D coordination polymers, [Mn 4(bcpb)4(N3)(H2O)4] n(ClO4)7n·nCH3OH· 3nH2O (2), [Mn2.5(bcpb)(N3)5(H 2O)2]n (3), [Mn2(bcpb)(N 3)4]n·nH2O (4), and [Mn 2(bcpb)(NCO)4]n·nH2O (5), were characterized. 2 is the first Mn(ii) compound with the rare μ4-1,1,3,3 azide bridge and exhibits an unusual 3D framework based on the [Mn4(μ4-1,1,3,3-N3)(μ-1,3-OCO) 6] cluster. In 3, the unique undulated honeycomb-like [Mn 2(μ-1,3-N3)3]n layers are interlinked into a 3D framework by disordered [Mn(μ-1,1-N3) 4(μ-1,3-OCO)2] and [(Oaqua-H) 2⋯OCO]2 moieties, and the bcpb ligands serve as additional interlayer linkers to lead to the rare self-catenated 66 net. 4 and 5 show 3-fold interpenetrated 3D frameworks based on the chains with (μ-1,1-N3)2(μ-1,3-OCO) and (μ-N,N-NCO) 2(μ-1,3-OCO) bridges, respectively. Magnetic studies indicated that 1 shows competing ferromagnetic and antiferromagnetic interactions. Compounds 2-5 all show antiferromagnetic coupling between Mn(ii) ions, while 3 shows 3D ordering. Analyses of magneto-structural data suggest a general trend that the antiferromagnetic interaction through (μ-1,1-N3) 2(μ-1,3-OCO) or (μ-N,N-NCO)2(μ-1,3-OCO) increases with a decrease of the Mn⋯Mn distance.
AB - The flexible zwitterionic dicarboxylate ligand 1,4-bis(4-carboxylato-1- pyridinium)butane (bcpb) assumes different conformations to collaborate with pseudohalides in various coordination modes to produce coordination polymers in which distinct anionic motifs with mixed carboxylate and pseudohalide bridges are interlinked by the cationic butylenebis(pyridinium) tethers. The Cu(ii) compound, [Cu2(bcpb)(N3)4]n·nH 2O (1), is a 1D coordination polymer based on the defective dicubane-like [Cu4(μ3-1,1,1-N3) 2(μ-1,1-N3)2(μ-1,1-OCO)2] cluster. With Mn(ii), four distinct 3D coordination polymers, [Mn 4(bcpb)4(N3)(H2O)4] n(ClO4)7n·nCH3OH· 3nH2O (2), [Mn2.5(bcpb)(N3)5(H 2O)2]n (3), [Mn2(bcpb)(N 3)4]n·nH2O (4), and [Mn 2(bcpb)(NCO)4]n·nH2O (5), were characterized. 2 is the first Mn(ii) compound with the rare μ4-1,1,3,3 azide bridge and exhibits an unusual 3D framework based on the [Mn4(μ4-1,1,3,3-N3)(μ-1,3-OCO) 6] cluster. In 3, the unique undulated honeycomb-like [Mn 2(μ-1,3-N3)3]n layers are interlinked into a 3D framework by disordered [Mn(μ-1,1-N3) 4(μ-1,3-OCO)2] and [(Oaqua-H) 2⋯OCO]2 moieties, and the bcpb ligands serve as additional interlayer linkers to lead to the rare self-catenated 66 net. 4 and 5 show 3-fold interpenetrated 3D frameworks based on the chains with (μ-1,1-N3)2(μ-1,3-OCO) and (μ-N,N-NCO) 2(μ-1,3-OCO) bridges, respectively. Magnetic studies indicated that 1 shows competing ferromagnetic and antiferromagnetic interactions. Compounds 2-5 all show antiferromagnetic coupling between Mn(ii) ions, while 3 shows 3D ordering. Analyses of magneto-structural data suggest a general trend that the antiferromagnetic interaction through (μ-1,1-N3) 2(μ-1,3-OCO) or (μ-N,N-NCO)2(μ-1,3-OCO) increases with a decrease of the Mn⋯Mn distance.
UR - https://www.scopus.com/pages/publications/84878661755
U2 - 10.1039/c3dt50460c
DO - 10.1039/c3dt50460c
M3 - 文章
AN - SCOPUS:84878661755
SN - 1477-9226
VL - 42
SP - 8748
EP - 8760
JO - Dalton Transactions
JF - Dalton Transactions
IS - 24
ER -