期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2010
卷号：107
期号：37
页码：16033-16038
DOI：10.1073/pnas.0910146107
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：The synthesis of the salt [IMG]/medium/pnas.0910146107eq1.gif" ALT="Formula "> 3 and metallo-organic framework (MOF) [{(4,4'-bipy)CoBr2}n] 4 by a range of solid state (mechanochemical and thermochemical) and solution methods is reported; they are isostructural with their respective chloride analogues 1 and 2. 3 and 4 can be interconverted by means of HBr elimination and absorption. Single phases of controlled composition and general formula [4,4'-H2bipy][CoBr4-xClx] 5x may be prepared from 2 and 4 by solid--gas reactions involving HBr or HCl respectively. Crystalline single phase samples of 5x and [{(4,4'-bipy)CoBr2-xClx}n] 6x were prepared by solid-state mechanochemical routes, allowing fine control over the composition and unit cell volume of the product. Collectively these methods enable continuous variation of the unit cell dimensions of the salts [4,4'-H2bipy][CoBr4-xClx] (5x) and the MOFs [{(4,4'-bipy)CoBr2-xClx}n] (6x) by varying the bromide to chloride ratio and establish a means of controlling MOF composition and the lattice metrics, and so the physical and chemical properties that derive from it.
