Linking chiral clusters with molybdate building blocks: from homochiral helical supramolecular arrays to coordination helices

Long, D.L. , Kögerler, P., Farrugia, L.J. and Cronin, L. (2006) Linking chiral clusters with molybdate building blocks: from homochiral helical supramolecular arrays to coordination helices. Chemistry: An Asian Journal, 1(3), pp. 352-357. (doi:10.1002/asia.200600069)

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Publisher's URL: http://doi.wiley.com/10.1002/asia.200600069

Abstract

The synthesis of four new oxo-centered Fe clusters (<b>1 a-c</b>, <b>2</b>) of the form [Fe<sup>III</sup><sub>3</sub>(<sub>µ 3</sub>-O)(CH<sub>2</sub>=CHCOO)<sub>6</sub>] with acrylate as the bridging ligand gives rise to potentially intrinsically chiral oxo-centered {M3} trimers that show a tendency to spontaneously resolve upon crystallization. For instance, 1 a, [Fe<sub>3</sub>(<sub>µ 3</sub>-O)(CH<sub>2</sub>=CHCOO)<sub>6</sub>] -(H<sub>2</sub>O)<sub>3</sub>]<sup>+</sup>, crystallizes in the chiral space group <i>P3<sub>1</sub></i> as a chloride salt. Crystallization of <b>1 b</b>, [Fe<sub>3</sub>(<sub>µ 3</sub>-O)(C<sub>2</sub>H<sub>3</sub>CO<sub>2</sub>)<sub>6</sub>(H<sub>2</sub>O)<sub>3</sub>]NO<sub>3</sub>4.5H<sub>2</sub>O, from aqueous solution followed by recrystallization from acetonitrile also gives rise to spontaneous resolution to yield the homochiral salt [Fe<sub>3</sub>(<sub>µ3</sub>-O)(C<sub>2</sub>H<sub>3</sub>CO<sub>2</sub>)<sub>6</sub>-(H<sub>2</sub>O)<sub>3</sub>]NO<sub>3</sub>CH<sub>3</sub>CN of <b>1 c</b> (space group P2<sub>1</sub>2<sub>1</sub>2<sub>1</sub>). Furthermore, the reaction of <b>1 a</b> with hexamolybdate in acetonitrile gives the helical coordination polymer {[(Fe<sub>3</sub>(<sub>µ3</sub>-O)L<sub>6</sub>(H<sub>2</sub>O))(MoO<sub>4</sub>)-(Fe<sub>3</sub>(<sub>µ3</sub>-O)L<sub>6</sub>(H<sub>2</sub>O)<sub>2</sub>)]2CH<sub>3</sub>CNH<sub>2</sub>O}<sub>∞</sub> <b>2</b> (L: H<sub>2</sub>C==CHCOO), which crystallizes in the space group <i>P</i>2<sub>1</sub>. The nature of the ligand geometry allows the formation of atropisomers in both the discrete (<b>1 a-c</b>) and linked {Fe<sub>3</sub>} clusters (<b>2</b>), which is described along with a magnetic analysis of <b>1 a</b> and <b>2</b>.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr Deliang and Cronin, Professor Lee
Authors: Long, D.L., Kögerler, P., Farrugia, L.J., and Cronin, L.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
University Centres > Glasgow Materials Research Initiative
Journal Name:Chemistry: An Asian Journal
ISSN:1861-4728

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