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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}
}
  • The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, even including corrections for the dispersion forces. In contrast, a multireferencemore » wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.« less
    Cited by 1
  • The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, even including corrections for the dispersion forces. In contrast, a multireferencemore » wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.« less
  • The host–guest interaction between metal ions (Pt 2+ and Cu 2+) and a zirconium metal–organic framework (UiO-66-NH2) was explored using dynamic nuclear polarization-enhanced 15N{1H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt 2+ coordinates with two NH2 groups from the MOF and two Cl - from the metal precursor, whereas Cu 2+ do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt 2+ prefers a square-planar structure with the four ligands and resides in the octahedral cage of themore » MOF in either cis or trans configurations.« less
  • The host–guest interaction between metal ions (Pt²⁺ and Cu²⁺) and a zirconium metal–organic framework (UiO-66-NH₂) was explored using dynamic nuclear polarization-enhanced ¹⁵N{¹H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt²⁺ coordinates with two NH₂ groups from the MOF and two Cl⁻ from the metal precursor, whereas Cu²⁺ do not form chemical bonds with the NH₂ groups of the MOF framework. Density functional calculations reveal that Pt²⁺ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or transmore » configurations.« less
  • Host–guest interactions between the aromatic molecules benzene, toluene, aniline and nitrobenzene and the redox-active TCNQ-based metal–organic framework (MOF), Fe(TCNQ)(4,4'-bpy) (1) (TCNQ = 7,7,8,8-tetracyanoquinodimethane), have been found to modulate spontaneous magnetization behaviours at low temperatures. An analogous MOF, Mn(TCNQ)(4,4'-bpy) (2) with isotropic Mn(II) ions as well as the two-dimensional compound Fe(TCNQ)(DMF)2·2DMF (3·2DMF), were also prepared as models for studying the effects of single-ion magnetic anisotropy and structural distortion on spin canting. The results indicate guest-dependent long range magnetic ordering occurs at low temperatures, which correlates with the electrostatic and steric effects of the incorporated aromatic guests.