Four tetrazolate-based 3D frameworks with diverse subunits directed by inorganic anions and azido coligand: hydro/solvothermal syntheses, crystal structures, and magnetic properties

被引:21
作者
Hou, Zhao-Jun [1 ]
Liu, Zhong-Yi [1 ]
Liu, Ning [1 ]
Yang, En-Cui [1 ]
Zhao, Xiao-Jun [1 ,2 ]
机构
[1] Tianjin Normal Univ, Tianjin Key Lab Struct & Performance Funct Mol, Key Lab Inorgan Organ Hybrid Funct Mat Chem, Coll Chem,Minist Educ, Tianjin 300387, Peoples R China
[2] Collaborat Innovat Ctr Chem Sci & Engn Tianjin, Tianjin 300071, Peoples R China
基金
中国国家自然科学基金;
关键词
METAL-ORGANIC FRAMEWORKS; GAS-ADSORPTION; SPIN-CROSSOVER; LINEAR-CHAIN; 1ST EXAMPLES; COORDINATION; LIGANDS; PHOTOLUMINESCENCE; TRANSFORMATION; LUMINESCENCE;
D O I
10.1039/c4dt03172e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Four tetrazolate (tz(-))-based magnetic metal-organic frameworks, [Cu-5(mu(3)-OH)(2)(SO4)(2)(tz)(4)](n) (1), {[Cu-3(tz)(4)Cl-2]center dot 1.4CH(3)OH}(n) (2), [Cu(N-3)(tz)](n) (3) and {[Cu-5(tz)(9)]Cl center dot 4H(2)O}(n) (4), were hydro/solvothermally synthesized, and structurally and magnetically characterized. Structural analyses reveal that the former two samples exhibit the same eight-connected topological framework assembled from different subunits. Hourglass-shaped {Cu-5(mu(3)-OH)(2)}(8+) cores in 1 are periodically extended by mixed mu(3)-/mu(4)-tz(-) and mu(4)-SO42- heterolinkers, while the linear {Cu-3(mu-Cl)(2)}(4+) blocks in 2 are repeatedly intersected by ditopic mu(3)-tz(-) connectors. In contrast, the square grid-shaped network of 3 is constructed from linear {Cu(mu(1,1)-N-3)}(+) chains and mu(3)-tz(-) linkers. Complex 4 consists of trigonal-prismatic {Cu-8(mu(3)-tz)(6)}(10+) subunits, which are interlinked into hexagonal microporous architecture by mirror-symmetry mu(4)-tz(-) ligands. Thus, the various subunits of 1-4 are significantly tuned by the co-coordination of the inorganic anions and/or the azido co-ligand, and the backbone extensions are directed by the polytopic tetrazolate ligand. Magnetically, different ordering arrangements of the non-zero magnetizations produced in the local Cu-5(II) and Cu-3(II) subunits eventually lead to unusual ferrimagnetic and canted antiferromagnetic properties in 1 and 2. Strong antiferromagnetic couplings mediated by the mixed tz(-) and/or azido bridges result in overall S = 0 spin ground-states of 3 and 4.
引用
收藏
页码:2223 / 2233
页数:11
相关论文
共 51 条
[1]   SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].
ADDISON, AW ;
RAO, TN ;
REEDIJK, J ;
VANRIJN, J ;
VERSCHOOR, GC .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356
[2]  
[Anonymous], 1996, SADABS
[3]  
[Anonymous], INFRARED ROMAN SPECT
[4]  
Bruker A.X.S., 1998, SAINT Software Reference Manual
[5]  
Carlin R.L., 1986, MAGNETOCHEMISTRY
[6]  
Carlucci L, 1999, ANGEW CHEM INT EDIT, V38, P3488
[7]   New Iron(II) Spin Crossover Coordination Polymers [Fe(μ-atrz)3] X2•2H2O (X = ClO4-, BF4-) and [Fe(μ-atrz)(μ-pyz)(NCS)2]•4H2O with an Interesting Solvent Effect [J].
Chuang, Yu-Chun ;
Liu, Chi-Tsun ;
Sheu, Chou-Fu ;
Ho, Wei-Lun ;
Lee, Gene-Hsiang ;
Wang, Chih-Cheh ;
Wang, Yu .
INORGANIC CHEMISTRY, 2012, 51 (08) :4663-4671
[8]   Multipoint Interactions Enhanced CO2 Uptake: A Zeolite-like Zinc-Tetrazole Framework with 24-Nuclear Zinc Cages [J].
Cui, Ping ;
Ma, Yu-Guang ;
Li, Huan-Huan ;
Zhao, Bin ;
Li, Jian-Rong ;
Cheng, Peng ;
Balbuena, Perla B. ;
Zhou, Hong-Cai .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (46) :18892-18895
[9]   The first in situ organosulfonate-templated 3-fold interpenetrating framework built from rare tetrahedral [Cu4(μ4-SO4)] SBUs [J].
Deng, Zhao-Peng ;
Zhu, Zhi-Biao ;
Zhang, Xian-Fa ;
Huo, Li-Hua ;
Zhao, Hui ;
Gao, Shan .
CRYSTENGCOMM, 2011, 13 (11) :3895-3899
[10]   Azide-Functionalized Lanthanide-Based Metal-Organic Frameworks Showing Selective CO2 Gas Adsorption and Postsynthetic Cavity Expansion [J].
Ganguly, Sumi ;
Pachfule, Pradip ;
Bala, Sukhen ;
Goswami, Arijit ;
Bhattacharya, Sudeshna ;
Mondal, Raju .
INORGANIC CHEMISTRY, 2013, 52 (07) :3588-3590