Design of single cyanide-bridged tetranuclear bimetallic rectangles exhibiting ferromagnetic coupling

Toma, Luminita Marilena; Lescouëzec, Rodrigue; Cangussu, Danielle; Llusar, Rosa; Mata, José A.; SharonSpey,; Thomas, Jim A.; Lloret, Francesc; Julve, Miguel

doi:10.1016/j.inoche.2004.12.031

Cited by 30 publications

(16 citation statements)

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“…6 The stability of the [Cu(bpca)(H 2 O) 2 ] + and [Cu(bpcam)-(H 2 O) 3 ] + species in solution together with the easy replacement of the coordinated water molecules by better donor atoms have made possible their use as Lewis bases against potential mono-or polyatomic bridges (organic linkers) and preformed complexes acting as donors in order to prepare homo-7-9 and heteropolymetallic compounds. 10,11 The isolation of the Hbpca monoprotic acid 12 conducted for the preparation of mononuclear compounds such as [M(bpca) x ] (m−x)+ (M = 3d metal ion). [12][13][14][15] Their use as ligands has afforded heterodinuclear complexes, 16 homo-and heterotrinuclear compounds, 12a,14b,17,18 chains 15,17b,19,20 as well as honeycomb layered materials 17b,21 whose magnetic properties have been investigated, some of them being examples of single molecule magnets (SMMs) 16,18 and single chain magnets (SCMs).…”

Section: Introductionmentioning

confidence: 99%

Copper(ii) assembling with bis(2-pyridylcarbonyl)amidate and N,N′-2,2-phenylenebis(oxamate)

et al. 2013

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We herein present the synthesis and X-ray structures of five copper(II) complexes of formulae [Cu(bpca)(CF3SO3)(H2O)]·H2O (1), [Cu(bpca)(Phpr)(H2O)]·3/2H2O (2), {[Cu(bpca)]2[Cu(opba)(H2O)]}·H2O (3), {[Cu(bpca)]2(H2opba)}2·6H2O (4) and [Cu(bpca)(EtH2opba)]n (5), where bpca = bis(2-pyridylcarbonyl)amidate, Phpr = 3-phenylpropionate, CF3SO3(−) = triflate (anion of the trifluoromethanesulphonic acid), H4opba = N,N′-1,2-phenylenebis(oxamic acid), and EtH3opba = monoethyl ester derivative of the H4opba. 1 and 2 are mononuclear copper(II) complexes where the copper atom is five-coordinate in distorted square pyramidal surroundings with a tridentate bpca and a water molecule (1)/carboxylate oxygen (2) building the basal plane and a triflate oxygen (1)/water molecule (2) filling the apical position. 3 is a neutral tricopper(II) complex where the [Cu(opba)(H2O)]2− unit acts as a bis-bidentate ligand toward two peripheral [Cu(bpca)]+ fragments. The three crystallographically independent copper(II) ions in 3 are five-coordinate with two nitrogen and two oxygen atoms (inner copper atom)/three bpca-nitrogen and an oxamate oxygen (outer copper atom) building the basal plane plus a water molecule (inner copper)/an oxamate oxygen (outer copper) in the apical position (inner copper atom) of somewhat distorted square pyramidal surroundings. 4 is a centrosymmetric tetracopper(II) compound where four [Cu(bpca)]+ fragments are assembled by two H2opba2− groups adopting an unusual bidentate/bis-monodentate bridging mode. The two crystallographically independent copper(II) ions in 4 are also five-coordinate having the three bpca-nitrogens in basal positions, the other two sites of the distorted square pyramid being filled by two oxygens of either a bidentate oxamate (at one copper centre) or two bis-monodentate oxamates (at the other copper atom). 5 is a zigzag chain of [Cu(bpca)(H2O)]+ units which are connected through the EtH2opba− ligand adopting a bidentate/monodentate bridging mode across the monodeprotonated oxamate group. Each copper(II) ion in 5 is six-coordinate in an elongated octahedral CuN3O3 chromophore. The magnetic properties of 3–5 were investigated in the temperature range 1.9–300 K. 3 exhibits an intermediate intramolecular antiferromagnetic interaction [J = -65.8(2) cm(-1) with the Hamiltonian H = -J(S(Cu1)·S(Cu2) + S(Cu2)·S(Cu3))] which leads to a low-lying spin doublet at low temperatures. A weak antiferromagnetic coupling between the inner copper(II) ions occurs in 4 [J = -2.36(2) cm(-1), H = -JS1·S2)] and a very small intrachain antiferromagnetic interaction is observed in 5 [J = -0.17(1) cm(-1) with H = -J∑(i)S(i)·S(i+1)]. These values are analyzed by means of simple orbital symmetry considerations and compared with those previously reported for parent systems.

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Section: Introductionmentioning

confidence: 99%

Copper(ii) assembling with bis(2-pyridylcarbonyl)amidate and N,N′-2,2-phenylenebis(oxamate)

et al. 2013

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“…It has been seen that the combination of pre-assembled Cu(II)-ligand unit with hexacyanoferrite [Fe(CN) 6 ] 3− yields a large number of coordination compounds in which the various structures and rich magnetic properties are mostly tuned by the peripheral ligands and/or solvents [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29]. It is surprising that the utilization of a third diamagnetic metal ion to tune the structures and properties of copper-hexacyanoferrite compounds is far less studied.…”

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Synthesis, crystal structures and magnetic properties of two three-dimensional heterotrimetallic compounds [Cu(en)2Li(H2O)][Fe(CN)6] and [Cu(en)2Li(H2O)][Co(CN)6] (en = ethylenediamine)

SiMa

Zhang

2011

Inorganic Chemistry Communications

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“…Generally, the utilization of multidentate O-and Ndonor ligands is an effective strategy to construct this kind of complex molecules. Hence, bpca (bis(2-pyridylcarbonyl)aminato) ligand is often used to prepare polynuclear complexes, (Lescouezec et al, 2005;Kamiyama et al, 2000;Kooijman et al, 2006;Kajiwara et al, 2002). However, investigations of the combination of bpca and dicarboxylate anions to design polynuclear ligands is limited.…”

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“…Tptz (2,4,6-Tripyridyl-1,3,5-triazine) will only hydrolyse in the presence of concentrated mineral acids and temperatures above 150°C (Smolin & Rapoport, 1959) or in the presence of Cu 2+ ions under mild conditions (Toma et al, 2005). In absence of any acids reaction of tptz and Cu 2+ produced [Cu(bpca)(tca)].2H 2 O (tca: 2-pyridinecarboxylate) (Zheng et al, 2006).…”

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μ-α-Methylglutarato-bis{aqua[bis(2-pyridylcarbonyl)aminato]copper(II)} trihydrate

Xie

Pan

et al. 2008

Acta Cryst E

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In the title compound, [Cu2(C12H8N3O2)2(C6H8O4)(H2O)2]·3H2O, both crystallographically independent Cu atoms are in similar distorted square-pyramidal coordination environments. The dinuclear complex molecules are assembled into one-dimensional supramolecular chains extending in the [100] direction by hydrogen bonds. Interchain hydrogen bonds further link these chains into layers perpendicular to [001].

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Design of single cyanide-bridged tetranuclear bimetallic rectangles exhibiting ferromagnetic coupling

Cited by 30 publications

References 16 publications

Copper(ii) assembling with bis(2-pyridylcarbonyl)amidate and N,N′-2,2-phenylenebis(oxamate)

Copper(ii) assembling with bis(2-pyridylcarbonyl)amidate and N,N′-2,2-phenylenebis(oxamate)

Synthesis, crystal structures and magnetic properties of two three-dimensional heterotrimetallic compounds [Cu(en)2Li(H2O)][Fe(CN)6] and [Cu(en)2Li(H2O)][Co(CN)6] (en = ethylenediamine)

μ-α-Methylglutarato-bis{aqua[bis(2-pyridylcarbonyl)aminato]copper(II)} trihydrate

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