Enlarging an Isoreticular Family: 3,3鈥?5,5鈥?Tetramethyl-4,4鈥?bipyrazolato-Based Porous Coordination Polymers

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• 作者：Aurel T膬b膬caru ; Claudio Pettinari ; Ivan Timokhin ; Fabio Marchetti ; Francisco Carrasco-Mar铆n ; Francisco Jos茅 Maldonado-H贸dar ; Simona Galli ; Norberto Masciocchi
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：July 3, 2013
• 年：2013
• 卷：13
• 期：7
• 页码：3087-3097
• 全文大小：561K
• 年卷期：v.13,no.7(July 3, 2013)
• ISSN：1528-7505

文摘

The solvothermal reaction between the rigid spacer 3,3鈥?5,5鈥?tetramethyl-4,4鈥?bipyrazole (H₂Me₄BPZ) and a number of transition metal salts promoted the formation of the coordination polymers [M(Me₄BPZ)] (M = Zn, 1; Co, 2; Cd, 3; Cu, 4). Ab initio X-ray powder diffraction analyses revealed the main structural aspects of the four materials. 1 and 2 are representative examples of the so-called isoreticular strategy: isostructural to [M(BPZ)] and [M(BDP)] (H₂BPZ = 4,4鈥?bipyrazole; H₂BDP = 1,4-bis(1H-pyrazol-4-yl)benzene), they feature three-dimensional (3-D) porous networks containing square-shaped channels. In 3, tetrahedral Cd(II) ions are arranged within homochiral helices reciprocally linked by radial Me₄BPZ spacers, overall creating a 3-D nonporous network. Finally, the 3-D porous framework of 4 comprises square Cu₄ nodes linked to eight neighboring ones by the bridging spacers. Thermogravimetric analyses, coupled to variable-temperature X-ray powder diffraction, demonstrated the remarkable thermal robustness of all the materials, decomposing above 300 掳C, and their stability for consecutive heating鈥揷ooling cycles. N₂ and CO₂ adsorption measurements at 77 and 273 K, respectively, were employed to probe the permanent porosity of the materials and to give a coherent picture of their textural properties including specific surface areas, micro- and mesopore volumes, as well as size distributions.