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含高铼酸根的微孔和开放骨架结构的合成与表征

Synthesis and characterization of ReO4-containing microporous and open framework structures.

作者信息

Luo Junhua, Alexander Ben, Wagner Timothy R, Maggard Paul A

机构信息

Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, NC 27695-8204, USA.

出版信息

Inorg Chem. 2004 Sep 6;43(18):5537-42. doi: 10.1021/ic049609h.

Abstract

A microporous and an open framework structure, [Cu(2)(pzc)(2)(H(2)O)(2)ReO(4)] (I) and [Cu(pzc)(H(2)O)ReO(4)].2H(2)O (II) (pzc = 2-pyrazinecarboxylate), respectively, have been prepared using hydrothermal methods and characterized using IR, TGA, and X-ray diffraction (I Pnma, No. 62, Z = 4, a = 7.4949(9) A, b = 24.975(3) A, c = 9.141(1) A; II P2(1)/c, No. 14, Z = 4, a = 8.5878(9) A, b = 12.920(1) A, c = 9.741(1) A, beta = 92.830(2) degrees ). I and II crystallize as red and blue solids, respectively, and each contains chains constructed from alternating Cu(pzc)(2)/ReO(4) oxide-bridged metal sites. The bidentate pzc ligand further bridges each -Cu-O-Re-O- chain to adjacent chains, via the Cu sites, to form a 3D net in I, with ellipsoidal channels that are approximately 3.3-4.7 A x 12.5 A, and in II, stacked layers of square nets with H(2)O-filled cavities that are approximately 4.4 x 5.1 A. Local ReO(4)(-) groups, a component of common oxidation catalysts, are directed at the channels and cavities of each structure, respectively. Thermogravimetric analysis indicates that I loses up to 64% of its H(2)O content before decomposition at 225 degrees C, while II loses approximately 100% of its H(2)O content by 265 degrees C.

摘要

分别采用水热法制备了微孔和开放框架结构的[Cu₂(pzc)₂(H₂O)₂ReO₄](I)和[Cu(pzc)(H₂O)ReO₄]·2H₂O(II)(pzc = 2 - 吡嗪羧酸盐),并通过红外光谱、热重分析和X射线衍射对其进行了表征(I:Pnma,编号62,Z = 4,a = 7.4949(9) Å,b = 24.975(3) Å,c = 9.141(1) Å;II:P2₁/c,编号14,Z = 4,a = 8.5878(9) Å,b = 12.920(1) Å,c = 9.741(1) Å,β = 92.830(2)°)。I和II分别结晶为红色和蓝色固体,且每个都包含由交替的Cu(pzc)₂/ReO₄氧化物桥连金属位点构成的链。双齿pzc配体通过Cu位点进一步将每个 -Cu - O - Re - O - 链桥连至相邻链,在I中形成三维网络,其椭圆形通道约为3.3 - 4.7 Å×12.5 Å,在II中形成具有填充H₂O的约4.4×5.1 Å空腔的方形网络堆叠层。常见氧化催化剂的组分局部ReO₄⁻基团分别指向每个结构的通道和空腔。热重分析表明,I在225℃分解前失去高达64%的水含量;而II在265℃时失去约100%的水含量。

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