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Title: Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules

Abstract

The physical properties of [CuL{sup 1} {sub 2}(H{sub 2}O)] (1) and [CuL{sup 2} {sub 2}(H{sub 2}O)] (2) and preparation and crystal structures of the inclusion compounds 1.(P)-C{sub 2}H{sub 4}Br{sub 2}, 2.(M)-C{sub 2}H{sub 4}Br{sub 2}, 1.CH{sub 3}CN and 2.CH{sub 3}CN are described. HL{sup 1} and HL{sup 2} (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-(R)-{alpha}-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-(S)-{alpha}-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuL {sup n} {sub 2}(H{sub 2}O)] (1 and 2) molecules connected by O-H...O and C-H...O interactions form perfectly polar two-dimensional networks. In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed (P) and the left-handed (M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C-H...O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O-H...O and C-H...O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules. -more » Graphical abstract: The square-pyramidal Cu(II) complexes [CuL {sup n} {sub 2}(H{sub 2}O)] with the bidentate HL {sup n} (HL{sup 1}=N-(2-hydroxy-5-nitrobenzyl)-(R)-{alpha}-methyl-benzylamine and HL{sup 2}=N-(2-hydroxy-5-nitrobenzyl)-(S)-{alpha}-methylbenzylamine) form 1:1 host-guest compounds with Br(CH{sub 2}){sub 2}Br and CH{sub 3}CN. The X-ray structures of these species reveal the enantiospecific confinement of the chiral rotamers of Br(CH{sub 2}){sub 2}Br and perfectly polar ordering of both host and guest molecules in the crystal lattice. The figure shows the polar alignments of (a) [CuL{sup 1} {sub 2}(H{sub 2}O)].(P)-C{sub 2}H{sub 4}Br{sub 2} and (b) [CuL{sup 2} {sub 2}(H{sub 2}O)].CH{sub 3}CN.« less

Authors:
 [1];  [1];  [2]
  1. School of Chemistry, University of Hyderabad, Hyderabad 500 046 (India)
  2. School of Chemistry, University of Hyderabad, Hyderabad 500 046 (India), E-mail: spsc@uohyd.ernet.in
Publication Date:
OSTI Identifier:
21015629
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.10.002; PII: S0022-4596(06)00543-3; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONITRILE; CHIRALITY; CLATHRATES; COPPER COMPLEXES; CRYSTAL LATTICES; ENANTIOMORPHS; INTERACTIONS; LIGANDS; PHENOLS; PHYSICAL PROPERTIES; PROTONS; SCHIFF BASES; SPACE GROUPS

Citation Formats

Muppidi, Vamsee Krishna, Zacharias, Panthapally S., and Pal, Samudranil. Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.10.002.
Muppidi, Vamsee Krishna, Zacharias, Panthapally S., & Pal, Samudranil. Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules. United States. doi:10.1016/j.jssc.2006.10.002.
Muppidi, Vamsee Krishna, Zacharias, Panthapally S., and Pal, Samudranil. Mon . "Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules". United States. doi:10.1016/j.jssc.2006.10.002.
@article{osti_21015629,
title = {Metal-organic frameworks from chiral square-pyramidal copper(II) complexes: Enantiospecific inclusion and perfectly polar alignment of guest and host molecules},
author = {Muppidi, Vamsee Krishna and Zacharias, Panthapally S. and Pal, Samudranil},
abstractNote = {The physical properties of [CuL{sup 1} {sub 2}(H{sub 2}O)] (1) and [CuL{sup 2} {sub 2}(H{sub 2}O)] (2) and preparation and crystal structures of the inclusion compounds 1.(P)-C{sub 2}H{sub 4}Br{sub 2}, 2.(M)-C{sub 2}H{sub 4}Br{sub 2}, 1.CH{sub 3}CN and 2.CH{sub 3}CN are described. HL{sup 1} and HL{sup 2} (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-(R)-{alpha}-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-(S)-{alpha}-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuL {sup n} {sub 2}(H{sub 2}O)] (1 and 2) molecules connected by O-H...O and C-H...O interactions form perfectly polar two-dimensional networks. In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed (P) and the left-handed (M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C-H...O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O-H...O and C-H...O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules. - Graphical abstract: The square-pyramidal Cu(II) complexes [CuL {sup n} {sub 2}(H{sub 2}O)] with the bidentate HL {sup n} (HL{sup 1}=N-(2-hydroxy-5-nitrobenzyl)-(R)-{alpha}-methyl-benzylamine and HL{sup 2}=N-(2-hydroxy-5-nitrobenzyl)-(S)-{alpha}-methylbenzylamine) form 1:1 host-guest compounds with Br(CH{sub 2}){sub 2}Br and CH{sub 3}CN. The X-ray structures of these species reveal the enantiospecific confinement of the chiral rotamers of Br(CH{sub 2}){sub 2}Br and perfectly polar ordering of both host and guest molecules in the crystal lattice. The figure shows the polar alignments of (a) [CuL{sup 1} {sub 2}(H{sub 2}O)].(P)-C{sub 2}H{sub 4}Br{sub 2} and (b) [CuL{sup 2} {sub 2}(H{sub 2}O)].CH{sub 3}CN.},
doi = {10.1016/j.jssc.2006.10.002},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}