Bis(pyrazolato)-Based Metal鈥揙rganic Frameworks Fabricated with 4,4鈥?Bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)biphenyl and Late Transition Metals

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• 作者：Aurel T膬b膬caru ; Claudio Pettinari ; Fabio Marchetti ; Simona Galli ; Norberto Masciocchi
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：June 4, 2014
• 年：2014
• 卷：14
• 期：6
• 页码：3142-3152
• 全文大小：499K
• 年卷期：v.14,no.6(June 4, 2014)
• ISSN：1528-7505

文摘

The reaction between the flexible, bis(pyrazolato)-based ligand 4,4鈥?bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)biphenyl (H₂DMPMB) and late transition metal ions allowed the isolation of the two series of thermally stable metal鈥搊rganic frameworks [M(DMPMB)] (M = Co, Zn, Cd) and [M₂(DMPMB)] (M = Cu, Ag). X-ray powder diffraction (XRPD) structure determinations demonstrated that the anti conformation adopted by the ligand, juxtaposed to its exo-tetradentate coordination mode, induces the formation of a 3-D architecture with nonpervious 1-D channels in the three isomorphous species [M(DMPMB)] and of corrugated 2-D layers in [Cu₂(DMPMB)]. Coupling thermogravimetric analyses and variable temperature XRPD highlighted that the five materials are thermally stable at least up to 300 掳C, both under nitrogen and in air, the Cd(II) derivative decomposing only at the remarkably high temperature of 500 掳C. No thermal event could be detected; all the materials preserve their structural motifs up to decomposition. The adsorption properties of the five compounds were assayed toward N₂ at 77 K: while no adsorption was observed for [Cd(DMPMB)], the other species possess estimated BET and Langmuir specific surface areas in the ranges 64(1)鈥?26(3) m²/g and 142(4)鈥?13(27) m²/g, respectively, thus being an example of the interesting phenomenon known as 鈥減orosity without pores鈥? Finally, the luminescence properties of the Zn(II), Cd(II), and Cu(I) derivatives were investigated.