Linking Chiral Clusters with Molybdate Building Blocks: From Homochiral Helical Supramolecular Arrays to Coordination Helices |
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Authors: | De‐Liang Long Paul Kgerler LouisJ Farrugia Leroy Cronin |
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Institution: | De‐Liang Long,Paul Kögerler,Louis?J. Farrugia,Leroy Cronin |
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Abstract: | The synthesis of four new oxo‐centered Fe clusters ( 1 a – c , 2 ) of the form FeIII3(μ3‐O)(CH2=CHCOO)6] 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 , FeIII3(μ3‐O)(CH2=CHCOO)6‐(H2O)3]+, crystallizes in the chiral space group P31 as a chloride salt. Crystallization of 1 b , Fe3(μ3‐O)(C2H3CO2)6(H2O)3]NO3?4.5H2O, from aqueous solution followed by recrystallization from acetonitrile also gives rise to spontaneous resolution to yield the homochiral salt Fe3(μ3‐O)(C2H3CO2)6‐(H2O)3]NO3?CH3CN of 1 c (space group P212121). Furthermore, the reaction of 1 a with hexamolybdate in acetonitrile gives the helical coordination polymer {(Fe3(μ3‐O)L6(H2O))(MoO4)‐(Fe3(μ3‐O)L6(H2O)2)]?2CH3CN?H2O}∞ 2 (L: H2C?CHCOO), which crystallizes in the space group P21. The nature of the ligand geometry allows the formation of atropisomers in both the discrete ( 1 a – c ) and linked {Fe3} clusters ( 2 ), which is described along with a magnetic analysis of 1 a and 2 . |
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Keywords: | atropisomerism crystal engineering helical structures polyoxometalates supramolecular chemistry |
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