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From Racemic Compound to Spontaneous Resolution: A Linker‐Imposed Evolution of Chiral [MnMo 9 O 32 ] 6− ‐Based Polyoxometalate Compounds
Author(s) -
Tan Huaqiao,
Li Yangguang,
Chen Weilin,
Liu Ding,
Su Zhongmin,
Lu Ying,
Wang Enbo
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901112
Subject(s) - imidazole , enantiomer , polyoxometalate , chemistry , molecule , crystallography , racemic mixture , chirality (physics) , stereochemistry , linker , chiral symmetry , catalysis , organic chemistry , physics , quantum mechanics , computer science , operating system , quark , nambu–jona lasinio model
Five compounds based on [MnMo 9 O 32 ] 6− : (Himi) 6 [MnMo 9 O 32 ] ( 1 ) (imi=imidazole), Na 2 (Himi) 4 [MnMo 9 O 32 ] ⋅ 2 H 2 O ( 2 ), Na 3 (Himi) 3 [MnMo 9 O 32 ] ( 3 ), D ‐NH 4 Mn 2.5 [MnMo 9 O 32 ] ⋅ 11 H 2 O ( 4 a ), and L ‐NH 4 Mn 2.5 [MnMo 9 O 32 ] ⋅ 11 H 2 O ( 4 b ) were prepared and characterized. X‐ray crystallographic analysis revealed that compounds 1 and 2 with imidazole molecules as linkers are racemic compounds; compound 3 is a racemic solid solution of Na + cations and the polyoxoanion [MnMo 9 O 32 ] 6− ; and compounds 4 a and 4 b are enantiomers. In compound 4 , the homochiral polyoxoanions [MnMo 9 O 32 ] 6− are connected by Mn 2+ cations to form a unique (4 5 ⋅ 6)(4 7 ⋅ 6 8 ) topology net framework. By adjusting the linkers from imidazole molecules to Na + and finally Mn 2+ cations, the chiral polyoxoanions [MnMo 9 O 32 ] 6− were changed from a racemic compound to a conglomerate. This means that spontaneous resolution can be efficiently realized by connecting homochiral polyoxoanions into one‐dimensional (1D), 2D, and 3D structures, with an emphasis on using appropriate linkers with substantial interaction strength, directionality, and enantioselectivity.