α- and β-bis(1,1,1-trifluoro-5,5-dimethyl-5-methoxyacetylacetonato)copper(II):: Transforming the dense polymorph into a versatile new microporous framework

被引:148
作者
Soldatov, DV
Ripmeester, JA
Shergina, SI
Sokolov, IE
Zanina, AS
Gromilov, SA
Dyadin, YA
机构
[1] Natl Res Council Canada, Steacie Inst Mol Sci, Ottawa, ON K1A 0R6, Canada
[2] Russian Acad Sci, Inst Chem Kinet & Combust, Novosibirsk 630090, Russia
[3] Russian Acad Sci, Inst Inorgan Chem, Novosibirsk 630090, Russia
关键词
D O I
10.1021/ja981443u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Bis(1,1,1-trifluoro-5,5-dimethyl-5-methoxy-acetylacetotato)copper(II) was prepared in two polymorphic modifications. The orthorhombic alpha-form is stable and densely packed, with four trans and four cis square bischelate building blocks per unit cell. These are connected through additional coordination bonds to form a dense polymer network. For the trigonal beta-form, the square bischelate complex units are present exclusively as the trans isomers. The distinctive assembly of these units results in a lattice with an open pore volume of about 17% that is accessible to a wide range of guests. The compound has a remarkably strong affinity for the porous beta-form as evident from the efficient alpha-to-beta conversion on contact not only with liquid guests but also with organic vapors at pressures well below the saturation pressure. Although the open beta-form is metastable, it has a remarkable kinetic stability, most likely because of the trans-to-cis isomerization that must accompany the beta-to-alpha transformation. Many sorbents play a dual role as stabilizing guest and as catalyst promoting the alpha-to-beta or beta-to-alpha conversion. Because of its versatile sorption properties and relative robustness. the beta-form of the complex can be classified as a novel organic zeolite mimic.
引用
收藏
页码:4179 / 4188
页数:10
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