title: A 3D Heterometallic Coordination Polymer Constructed by Trimeric {NiDy2} Single-Molecule Magnet Units.
abstract: The solvothermal reaction of DyCl3·6H2O, Ni(NO3)2·6H2O, and H4abtc ligands (H4abtc = 3,3',5,5'-azobenzene-tetracarboxylic acid) in the mixed DMF/H2O solvents (DMF = N,N-dimethylformamide) produced a three-dimensional (3D) Ni(II)-Dy(III) heterometallic coordination polymer (HCP) formulated as {[NH2(CH3)2]2[NiDy2(HCOO)2(abtc)2]}n (1). In 1, Dy(III) and Ni(II) ions interconnect through carboxylic O donors of abtc(4-) ligands to generate a linear trimer "Hourglass"-type {NiDy2} cluster, and the adjacent trinuclear {NiDy2} units are bridged by HCOO(-) groups to give a 1D "ladder" chain, which is further bridged by abtc(4-) ligands to form a new topology and named as "zsw3". Alternating-current magnetic susceptibility results indicate that 1 exhibits frequency-dependent out-of-phase signals with two relaxation processes, which suggests that it shows single-molecule magnet (SMM) behavior and represents the first example by using an SMM cluster as the building block to create a 3D Ni-Ln HCP, to the best of our knowledge. The energy barriers for 1 under a 1000 Oe applied direct current magnetic field are estimated from Arrhenius plots to be 40 and 42 K at higher and lower frequencies, respectively. Additionally, the crystalline structure of 1 could be stable to at least 310 °C, supported by thermogravimetric analyses and in situ variable-temperature powder X-ray diffraction patterns.
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.|Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of the Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology , Xiangtan 411201, P. R. China.
authors.forename: Shaowei
authors.initials: S
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.
authors.forename: Han
authors.initials: H
authors.lastname: Li
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.
authors.forename: Eryue
authors.initials: E
authors.lastname: Duan
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.
authors.forename: Zongsu
authors.initials: Z
authors.lastname: Han
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.
authors.forename: Leilei
authors.initials: L
authors.lastname: Li
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , Changchun, 130022, P. R. China.
authors.forename: Jinkui
authors.initials: J
authors.lastname: Tang
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.|Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, P. R. China.
authors.forename: Wei
authors.initials: W
authors.lastname: Shi
authors.affiliation: Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University , Tianjin 300071, P. R. China.|Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, P. R. China.
authors.forename: Peng
authors.initials: P
authors.lastname: Cheng