Novel Coordination Frameworks Incorporating the 4,4鈥?Bipyrazolyl Ditopic Ligand
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- 作者：Claudio Pettinari ; Aurel T膬b膬caru ; Ishtvan Boldog ; Konstantin V. Domasevitch ; Simona Galli ; Norberto Masciocchi
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：May 7, 2012
- 年：2012
- 卷：51
- 期：9
- 页码：5235-5245
- 全文大小：550K
- 年卷期：v.51,no.9(May 7, 2012)
- ISSN：1520-510X
文摘
The reaction of the rigid spacer 4,4鈥?bipyrazole (H2BPZ) with late transition metals, either following conventional routes or under solvothermal conditions, afforded the coordination polymers [M(BPZ)]路Solv (M = Zn, 1; Co, 2; Cd, 3; Hg, 4; Cu, 5; Ni, 6; Pd, 7; Solv = DMF, 3; MeCN, 5 and 6; H2O, 7), [Cu(H2BPZ)2(NO3)2] (8), and [Cd(H2BPZ)(CH3COO)2] (9). State-of-the-art laboratory powder diffraction methods allowed to disclose the isomorphous character of 1 and 2, as well as of 5 and 6, which feature 3D porous networks containing 1D channels of square and rhombic shape, respectively. 3, crystallizing in the relatively rare P6122 space group, consists of homochiral helices of octahedral CdII ions, packing in bundles mutually linked by 鈥渞adial鈥? nonplanar BPZ ligands. Finally, the dense species 8 and 9 contain parallel 2D layers of square and rectangular meshes, respectively. Thermogravimetric analyses witnessed the relevant thermal robustness of all the [M(BPZ)] materials [except the mercury(II) derivative], which are stable in air at least up to 300 掳C, with the zinc(II) derivative decomposing only around 450 掳C. Variable-temperature powder diffraction experiments highlighted the permanent porosity of 1鈥?b>3, 5, and 6, retained along consecutive temperature cycles in all cases but 3. When probed with N2 at 77 K, 1鈥?b>3 and 5鈥?b>7 showed Brunauer鈥揈mmett鈥揟eller and Langmuir specific surface areas in the ranges 314(2)鈥?93(11) and 509(16)鈥?105(1) m2/g, respectively.