Two- and Three-Dimensional Cadmium-Organic Frameworks with Trimesic Acid and 4,4'-Trimethylenedipyridine
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- 作者：Filipe A. Almeida Paz and Jacek Klinowski
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：June 28, 2004
- 年：2004
- 卷：43
- 期：13
- 页码：3882 - 3893
- 全文大小：847K
- 年卷期：v.43,no.13(June 28, 2004)
- ISSN：1520-510X
文摘
Three novel cadmium-organic frameworks built-up from 1,3,5-benzenetricarboxylate anions (HXBTCx-3) and4,4'-trimethylenedipyridine (TMD) have been hydrothermally synthesized, and characterized using single-crystalX-ray diffraction, thermoanalytical measurements, elemental analysis, and IR and Raman spectroscopies:[Cd(HBTC)(TMD)2]·8.5H2O (I), [Cd(HBTC)(TMD)(H2O)]·4.5H2O (II), and [Cd2(BTC)(TMD)2(NO3)]·3H2O (III), withstructures I and II being isolated as a mixture of crystals. Structure I contains an undulating infinite two-dimensional[Cd(HBTC)(TMD)2] framework, with a (4,4) topology and rectangular pores, ca. 3.4 × 11.0 Å in cross-section,distributed in a herringbone manner. The crystal structure of I is obtained by parallel packing of this 2D frameworkin an [ABAB···] fashion. Compound II has a porous 3D diamondoid framework with channels running in severaldirections of the unit cell, which allows 2-fold interpenetration to occur. The most prominent channels are distributedin a brick-wall fashion along the c axis and have a cross-section of ca. 3.2 × 13.2 Å. Structure III can be seen asthe three-dimensional assembly of binuclear secondary building units (SBU), which leads to a compact, neutral,and coordinatively bonded eight-connected framework, [Cd2(BTC)(TMD)2(NO3)], exhibiting an unusual 36422 topology.The increased flexibility of the TMD ligands (brought about by the three methylene groups between the two 4-pyridylrings) can lead, for the same reactive system, to a large variety of crystal architectures.