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Title: Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

Abstract

Three novel tetranuclear copper(II) complexes namely [Cu{sub 4}(L{sup 1}){sub 4}]∙2(dmf) (1), [Cu{sub 4}(L{sup 1}){sub 4}] (2) and [Cu{sub 4}(L{sup 2}){sub 2}(HL{sup 2}){sub 2}(H{sub 2}O){sub 2}]∙2(ClO{sub 4})·6(H{sub 2}O) (3) (H{sub 2}L{sup 1}, (E)−2-((1-hydroxybutan-2-ylimino)methyl)phenol; H{sub 2}L{sup 2}, (E)−2-((1-hydroxybutan-2-ylimino)methyl)−6-methoxyphenol)) were synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that crystallizes in the monoclinic system with space group C2/c, whereas both the and crystallize in the triclinic system with space group P-1. and possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π…π and C–H…π interactions lead to formation of a 2D supramolecular architecture for and . At room temperature and , exhibit fluorescence with a quantum yield (Φ{sub s}) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2–300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H =– J{sub 1}(S{sub 1}S{sub 2}+S{sub 1}S{sub 2’}+S{sub 1'}S{sub 2}+S{sub 1'}S{sub 2’}) – J{sub 2}S{submore » 1}S{sub 1’}, where S{sub 1} = S{sub 1’} = S{sub 2} = S{sub 2’} = S{sub Cu} =1/2, was used for studying and . Simulations performed suggest magnetic exchange constants with values close to J{sub 1} =−20 cm{sup −1} and J{sub 2} =0 cm{sup -1} for these complexes. On the other hand, the spin Hamiltonian H =– J{sub 1}(S{sub 1}S{sub 4}+S{sub 2}S{sub 3}) – J{sub 2}(S{sub 1}S{sub 3}+S{sub 2}S{sub 4}) – J{sub 3}S{sub 1}S{sub 2}, where S{sub 1} = S{sub 2} = S{sub 3} = S{sub 4} = S{sub Cu} =1/2, was used to study the magnetic behaviour of the double open cubane core of and a good agreement between the experimental and simulated results was found by using the parameters g{sub 1} = g{sub 2} =2.20, g{sub 3} = g{sub 4} =2.18, J{sub 1} =−36 cm{sup -1}, J{sub 2} =−44 cm{sup -1} and J{sub 3} =0 cm{sup -1}. - Graphical abstract: Tetranuclear Cu(II) complexes with face-sharing-dicubane / double-open-cubane like core frameworks were synthesized and characterized by crystal structure and magnetic analysis. Variable temperature magnetic properties corroborate with their structural arrangement. - Highlights: • Novel tetranuclear copper(II) complexes have been structurally characterized. • Complexes possess face-sharing dicubane/double open cubane core structures. • Variable temperature magnetic measurements reveal antiferromagnetic coupling. • PHI program was used to explain the observed magnetic properties.« less

Authors:
 [1];  [2];  [3];  [1]
  1. Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721102, West Bengal (India)
  2. Dipartimento di Scienze Chimiche e Farmaceutiche, Centro di Strutturistica Diffrattometrica, Università di Ferrara, Via L. Borsari, 46, 44100 Ferrara (Italy)
  3. Departament de Química Inorgànica i Orgànica (Secció de Química Inorgànica) and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain)
Publication Date:
OSTI Identifier:
22658257
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 249; Other Information: Copyright (c) 2017 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; COMPLEXES; COPPER IONS; EXPERIMENTAL DATA; MAGNETIC SUSCEPTIBILITY; METHYL RADICALS; MONOCLINIC LATTICES; PHENOL; SCHIFF BASES; SPACE GROUPS; SYNTHESIS

Citation Formats

Paul, Aparup, Bertolasi, Valerio, Figuerola, Albert, and Manna, Subal Chandra, E-mail: scmanna@mail.vidyasagar.ac.in. Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.02.009.
Paul, Aparup, Bertolasi, Valerio, Figuerola, Albert, & Manna, Subal Chandra, E-mail: scmanna@mail.vidyasagar.ac.in. Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework. United States. doi:10.1016/J.JSSC.2017.02.009.
Paul, Aparup, Bertolasi, Valerio, Figuerola, Albert, and Manna, Subal Chandra, E-mail: scmanna@mail.vidyasagar.ac.in. Mon . "Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework". United States. doi:10.1016/J.JSSC.2017.02.009.
@article{osti_22658257,
title = {Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework},
author = {Paul, Aparup and Bertolasi, Valerio and Figuerola, Albert and Manna, Subal Chandra, E-mail: scmanna@mail.vidyasagar.ac.in},
abstractNote = {Three novel tetranuclear copper(II) complexes namely [Cu{sub 4}(L{sup 1}){sub 4}]∙2(dmf) (1), [Cu{sub 4}(L{sup 1}){sub 4}] (2) and [Cu{sub 4}(L{sup 2}){sub 2}(HL{sup 2}){sub 2}(H{sub 2}O){sub 2}]∙2(ClO{sub 4})·6(H{sub 2}O) (3) (H{sub 2}L{sup 1}, (E)−2-((1-hydroxybutan-2-ylimino)methyl)phenol; H{sub 2}L{sup 2}, (E)−2-((1-hydroxybutan-2-ylimino)methyl)−6-methoxyphenol)) were synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that crystallizes in the monoclinic system with space group C2/c, whereas both the and crystallize in the triclinic system with space group P-1. and possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π…π and C–H…π interactions lead to formation of a 2D supramolecular architecture for and . At room temperature and , exhibit fluorescence with a quantum yield (Φ{sub s}) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2–300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H =– J{sub 1}(S{sub 1}S{sub 2}+S{sub 1}S{sub 2’}+S{sub 1'}S{sub 2}+S{sub 1'}S{sub 2’}) – J{sub 2}S{sub 1}S{sub 1’}, where S{sub 1} = S{sub 1’} = S{sub 2} = S{sub 2’} = S{sub Cu} =1/2, was used for studying and . Simulations performed suggest magnetic exchange constants with values close to J{sub 1} =−20 cm{sup −1} and J{sub 2} =0 cm{sup -1} for these complexes. On the other hand, the spin Hamiltonian H =– J{sub 1}(S{sub 1}S{sub 4}+S{sub 2}S{sub 3}) – J{sub 2}(S{sub 1}S{sub 3}+S{sub 2}S{sub 4}) – J{sub 3}S{sub 1}S{sub 2}, where S{sub 1} = S{sub 2} = S{sub 3} = S{sub 4} = S{sub Cu} =1/2, was used to study the magnetic behaviour of the double open cubane core of and a good agreement between the experimental and simulated results was found by using the parameters g{sub 1} = g{sub 2} =2.20, g{sub 3} = g{sub 4} =2.18, J{sub 1} =−36 cm{sup -1}, J{sub 2} =−44 cm{sup -1} and J{sub 3} =0 cm{sup -1}. - Graphical abstract: Tetranuclear Cu(II) complexes with face-sharing-dicubane / double-open-cubane like core frameworks were synthesized and characterized by crystal structure and magnetic analysis. Variable temperature magnetic properties corroborate with their structural arrangement. - Highlights: • Novel tetranuclear copper(II) complexes have been structurally characterized. • Complexes possess face-sharing dicubane/double open cubane core structures. • Variable temperature magnetic measurements reveal antiferromagnetic coupling. • PHI program was used to explain the observed magnetic properties.},
doi = {10.1016/J.JSSC.2017.02.009},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 249,
place = {United States},
year = {Mon May 15 00:00:00 EDT 2017},
month = {Mon May 15 00:00:00 EDT 2017}
}
  • Two tetranuclear Mn complexes with an average Mn oxidation state of +2.5 have been prepared. These valence isomers have been characterized by a combination of X-ray crystallography, X-ray absorption spectroscopy, and magnetic susceptibility. The Mn{sup II}{sub 3}Mn{sup IV} tetramer has the Mn ions arranged in a distorted tetrahedron, with an S = 6 ground spin state, dominated by ferromagnetic exchange among the manganese ions. The Mn{sup II}{sub 2}Mn{sup III}{sub 2} tetramer also has a distorted tetrahedral arrangement of Mn ions but shows magnetic behavior, suggesting that it is a single-molecule magnet. The X-ray absorption near-edge structure (XANES) spectra for themore » two complexes are similar, suggesting that, while Mn XANES has sufficient sensitivity to distinguish between trinuclear valence isomers (Alexiou et al. Inorg. Chem. 2003, 42, 2185), similar distinctions are difficult for tetranuclear complexes such as that found in the photosynthetic oxygen-evolving complex.« less
  • Three new tetranuclear copper(II) cluster-based complexes constructed from 4-amino-1,2,4-triazole (atrz) and three types of aromatic carboxylates, [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(DNBA){sub 6}] (1), [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(1,3-BDC){sub 3}]{center_dot}2H{sub 2}O (2) and [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(SIP){sub 2}]{center_dot}4H{sub 2}O (3) (HDNBA=3,5-dinitrobenzoic acid, 1,3-H{sub 2}BDC=1,3-benzenedicarboxylic acid and NaH{sub 2}SIP=sodium 5-sulfoisophthalate), have been hydrothermally synthesized and structurally characterized. Complex 1 displays a single-molecular Cu{sup II}{sub 4} cluster structure, which is further connected by the intermolecular hydrogen-bonding interactions to form a 2D supramolecular layer. In 2, there also exist tetranuclear Cu{sup II}{sub 4} clusters, which are linked by the 1,3-BDC anions to givemore » a 3D NaCl-type framework. In 3, the Cu{sup II}{sub 4} clusters are connected by the carboxyl and sulfo groups of SIP anions to generate 3D (4,8)-connected framework with a (4{sup 10}{center_dot}6{sup 14}{center_dot}8{sup 4})(4{sup 5}{center_dot}6){sub 2} topology. The atrz ligand conduces to the construction of tetranuclear copper(II) clusters and the carboxylates with different non-carboxyl substituent show important effects on the final structures of the title complexes. The electrochemical and magnetic properties of 1-3 have been investigated. - Graphical abstract: Three tetranuclear copper(II) cluster-based complexes based on different carboxylates have been synthesized under hydrothermal conditions. The carboxylate anions play a key role in the formation of three different structures. Highlights: Black-Right-Pointing-Pointer Three new tetranuclear copper(II) cluster-based complexes have been obtained. Black-Right-Pointing-Pointer The atrz conduces to the construction of tetranuclear copper(II) clusters. Black-Right-Pointing-Pointer Carboxylates show important effect on the structures of title complexes. Black-Right-Pointing-Pointer Magnetic properties and electrochemical behaviors have been reported.« less
  • Several new synthetic methods have been developed for preparation of the rectangular tetrameric cluster complexes Mo/sub 4/X/sub 8/L/sub 4/ (X = Cl, Br, I; L = neutral donor ligand). Mo/sub 4/Cl/sub 8/(CH/sub 3/OH)/sub 4/ is prepared efficiently from the dimer Mo/sub 2/Cl/sub 4/(PPh/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ and subsequently converted in good yield to Mo/sub 4/Cl/sub 8/(C/sub 2/H/sub 5/CN)/sub 4/ by reaction with propionitrile. Reaction of Mo/sub 4/Cl/sub 8/(C/sub 2/H/sub 5/CN)/sub 4/ with triphenylphosphine yields Mo/sub 4/Cl/sub 8/(PPh/sub 3/)/sub 4/, and with tetrahydrofuran the unstable Mo/sub 4/Cl/sub 8/(THF)/sub 4/ is afforded. The trialkylphosphine derivatives Mo/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ (Rmore » = C/sub 2/H/sub 5/ or C/sub 4/H/sub 9/) may be obtained more conveniently in reactions between (a) K/sub 4/Mo/sub 2/Cl/sub 8/ + PR/sub 3/ (1:2 mole ratio), (b) Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ + PR/sub 3/ + (CH/sub 3/)/sub 3/SiCl (1:2:4 mole ratio), (c) Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ + PR/sub 3/ + AlCl/sub 3/ (1:2:2 mole ratio), or (d) Mo/sub 2/Cl/sub 4/(PR/sub 3/)/sub 4/ + Mo(CO)/sub 6/ (1:1 mole ratio). The Mo/sub 4/Br/sub 8/(P-n-Bu/sub 3/)/sub 4/ prepared by analogous methods exhibits properties closely related to the chloride derivative; Mo/sub 4/I/sub 8/(P-n-Bu/sub 3/)/sub 4/ however appears to consist of weakly coupled quadruply bonded dimers. The various compounds have been characterized by UV-visible, infrared, and Cl 2p photoelectron spectra which reflect the basic rectangular cluster structure known for Mo/sub 4/Cl/sub 8/(PEt/sub 3/)/sub 4/.« less
  • The syntheses, crystal structures, and magnetic properties of two new copper(II) complexes with molecular formulas [Cu 72-OH 2) 63-O) 6(adenine) 6(NO 3) 26H 2O (1) and [Cu 22-H 2O) 2(adenine) 2(H 2O) 4](NO 3) 42H 2O (2) are reported. We composed the heptanuclear compound of a central octahedral CuO 6 core sharing edges with six adjacent copper octahedra. In 2, the copper octahedra shares one equatorial edge. In both compounds, these basic copper cluster units are further linked by water bridges and bridging adenine ligands through N3 and N9 donors. All copper(II) centers exhibit Jahn-Teller distorted octahedralmore » coordination characteristic of a d 9 center. Our study of the magnetic properties of the heptacopper complex revealed a dominant ferromagnetic intra-cluster interaction, while the dicopper complex exhibits antiferromagnetic intra-dimer interactions with weakly ferromagnetic inter-dimer interaction.« less
  • To systematically explore the influence of inorganic anions on building coordination complexes, five novel complexes based on 1-(benzotriazole-1-methyl)−2-propylimidazole (bpmi), [Cu(bpmi){sub 2}(Ac){sub 2}]·H{sub 2}O (1), [Cu(bpmi){sub 2}(H{sub 2}O){sub 2}]·2NO{sub 3}·2H{sub 2}O (2), [Cu(bpmi)(N{sub 3}){sub 2}] (3), [Ag(bpmi)(NO{sub 3})] (4) and [Cu{sub 3}(bpmi){sub 2}(SCN){sub 4}(DMF)] (5) (Ac{sup −}=CH{sub 3}COO{sup −}, DMF=N,N-Dimethylformamide) are synthesized through rationally introducing Cu(II) salts and Ag(I) salt with different inorganic anions. X-ray single-crystal analyses reveal that these complexes show interesting structural features from mononuclear (1), one-dimensional (2 and 3), two-dimensional (4) to three-dimensional (5) under the influence of inorganic anions with different basicities. The structural variation can bemore » explained by the hard-soft-acid-base (HSAB) theory. Magnetic susceptibility measurement indicates that complex 3 exhibits an antiferromagnetic coupling between adjacent Cu(II) ions. - Graphical abstract: Five new Cu(II)/Ag(I) complexes show interesting structural features from mononuclear, one-dimension, two-dimension to three-dimension under the influence of inorganic anions. The structural variation can be explained by the HSAB theory. - Highlights: • Five inorganic anion-dependent complexes are synthesized. • Structural variation can be explained by the hard-soft-acid-base (HSAB) theory. • The magnetic property of complex has been studied.« less