Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 28, Pages 11376-11379Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja304371j
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Funding
- EPSRC
- Chinese Scholarship Council
- University of Glasgow
- Royal Society of Edinburgh
- Marie Curie Actions
- Royal Society/Wolfson Foundation
- EPSRC [EP/H024107/1, EP/F016360/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F016360/1, EP/H024107/1] Funding Source: researchfish
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Using [Mo2S2O2(H2O)(6)](2+) and squarate dianion, we synthesized the thiometalate ring compounds [(Mo2S2O2)(x)(OH)(y)(C4O4)(z)(Mo2O8)(o)(H2O)(p)](n-), where [x,y,z,o,p,n] = [7,14,2,0,2,4] for 1, [6,8,2,2,4,8] for 2, and [4,6,1,1,0,4] for both 3a and 3b, which are chiral and nonchiral isomers, respectively. Not only do the four thiometalate clusters show decreasing symmetry at the molecular level across the series, but the incorporation of the addendum {Mo2O8}(o) unit also allows the thiometalate ring to twist. The reaction initially yields the chiral molecule 3a with a twisted ring, which undergoes spontaneous resolution upon crystallization; the reaction mixture later yields the intrinsically nonchiral isomer 3b with a nontwisted ring. In addition, the compounds are able to promote the electrocatalytic evolution of hydrogen.
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