Towards polymorphism control in coordination networks and metallo-organic salts

Christopher J. Adams, Amy L. Gillon, Matteo Lusi, A. Guy Orpen

Research output: Contribution to journalArticlepeer-review

Abstract

[{(4,4′-bipy)ZnCl2}n] (4) is known in three different polymorphs, in the space groups C2/c (4a), Pnma (4b) and Pban (4c). Solution synthesis produces a mixture of 4a and 4b, but solid-state synthesis, either by grinding together 4,4′-bipy and ZnCl2 or by heating [4,4′-H2bipy][ZnCl4] 3 to thermally eliminate HCl, generates only the 4b form, demonstrating that solid-state synthesis can exert control over polymorph formation; other solid-state preparations of 4 such as reaction of basic zinc carbonate with [4,4′-H2bipy]Cl 2 or reaction of [4,4′-H2bipy][ZnCl4] 3 with KOH also increase the amount of 4b generated relative to the solution synthesis. It is also possible to form the mixed-metal phases [{(4,4′-bipy)Co1-xZnxCl2}n] 4x as effectively homogeneous solid-solutions by the same techniques, and when x < 0.5 (i.e. there is more cobalt present than zinc) then only the Pban polymorph of the solid-solution is observed. When x > 0.5, the amount of this polymorph is still greater than would be expected for a predominantly zinc-containing phase.

Original languageEnglish
Pages (from-to)4403-4409
Number of pages7
JournalCrystEngComm
Volume12
Issue number12
DOIs
Publication statusPublished - Dec 2010
Externally publishedYes

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