A pair of 3D enantiotopic zinc(ii) complexes based on two asymmetric achiral ligands. Issue 43 (17th October 2017)

• Record Type: Journal Article
• Authors: Zhang, Ming-Dao; Li, Yan-Le; Shi, Zhen-Zhen; Zheng, He-Gen; Ma, Jing
• Is Part Of: Dalton transactions. Volume 46:Issue 43(2017)
• Page Start: 14779
• Page End: 14784
• Publication Date: 2017-10-17
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt03205f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Two 3D enantiotopic chiral metal–organic frameworks, with ferroelectric behaviors and second-order nonlinear optical effects, were constructed based on achiral ligands in one pot with high enantiomeric excess owing to the hydrogen bonds. Abstract : Enantiomorphism and enantioselectivity are critical in biology and many other applications. Herein, we report two 3D chiral MOFs {[Zn6 (MIDPPA)3 (1, 2, 4-btc)3 (NO2 )3 (H2 O)3 ](H2 O)7 } n (1L and1R ) based on achiral ligands with high enantiomeric excess and a novel topological type. The internal mechanism of spontaneous chiral symmetry breaking, during the crystallization of chiral MOFs based on achiral ligands, is elucidated for the first time from both structural and theoretical aspects. Hydrogen bonds are found to play a key role in the spontaneous symmetry breaking of chiral MOFs. Also, DFT calculations support our findings from the aspects of total energies and HOMO–LUMO energy gaps. Both1L and1R, exhibiting green fluorescence, present a non-centrosymmetric polar packing arrangement, resulting in good ferroelectric behaviors and second-order nonlinear optical effects.