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Linking Chiral Clusters with Molybdate Building Blocks: From Homochiral Helical Supramolecular Arrays to Coordination Helices
Author(s) -
Long DeLiang,
Kögerler Paul,
Farrugia Louis J.,
Cronin Leroy
Publication year - 2006
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200600069
Subject(s) - acetonitrile , chemistry , supramolecular chemistry , crystallography , aqueous solution , enantiomer , ligand (biochemistry) , molybdate , crystallization , chiral resolution , chirality (physics) , stereochemistry , crystal structure , inorganic chemistry , organic chemistry , physics , biochemistry , receptor , nambu–jona lasinio model , chiral symmetry breaking , quantum mechanics , quark
The synthesis of four new oxo‐centered Fe clusters ( 1 a – c , 2 ) of the form [Fe III 3 (μ 3 ‐O)(CH 2 =CHCOO) 6 ] with acrylate as the bridging ligand gives rise to potentially intrinsically chiral oxo‐centered {M 3 } trimers that show a tendency to spontaneously resolve upon crystallization. For instance, 1 a , [Fe III 3 (μ 3 ‐O)(CH 2 =CHCOO) 6 ‐(H 2 O) 3 ] + , crystallizes in the chiral space group P 3 1 as a chloride salt. Crystallization of 1 b , [Fe 3 (μ 3 ‐O)(C 2 H 3 CO 2 ) 6 (H 2 O) 3 ]NO 3 ⋅4.5H 2 O, from aqueous solution followed by recrystallization from acetonitrile also gives rise to spontaneous resolution to yield the homochiral salt [Fe 3 (μ 3 ‐O)(C 2 H 3 CO 2 ) 6 ‐(H 2 O) 3 ]NO 3 ⋅CH 3 CN of 1 c (space group P 2 1 2 1 2 1 ). Furthermore, the reaction of 1 a with hexamolybdate in acetonitrile gives the helical coordination polymer {[(Fe 3 (μ 3 ‐O)L 6 (H 2 O))(MoO 4 )‐(Fe 3 (μ 3 ‐O)L 6 (H 2 O) 2 )]⋅2CH 3 CN⋅H 2 O} ∞ 2 (L: H 2 CCHCOO), which crystallizes in the space group P 2 1 . The nature of the ligand geometry allows the formation of atropisomers in both the discrete ( 1 a – c ) and linked {Fe 3 } clusters ( 2 ), which is described along with a magnetic analysis of 1 a and 2 .