A methylene-bridged 1-hydroxybenzotriazole derived ligand L [L = 1, 3-bis(benzotriazol-1-yl)-1,3-dioxapropane] has been synthesized and characterized by spectroscopic and structural methods. Reaction of L with two different copper(II) halides [CuX2; X = Br, Cl] in an identical condition yields two different compounds of similar compositions, {[Cu(μ-Br)(Br)(μ-L)]2}n·2nH2O (1) and {[Cu(μ-Cl)(Cl)(μ-L)]2}n·2nH2O (2), both being characterized by various physicochemical techniques. Single crystal X-ray studies reveal that they appear as 2D coordination polymers with similar bridging fashion of L. Low temperature magnetic susceptibility measurements reveal antiferromagnetic and ferromagnetic behaviors for 1 and 2 with magnetic coupling constants J = −15.2 and +1.7 cm–1, which are in a reasonable agreement with their calculated values (J = −9.79 and +0.68 cm–1 respectively, for 1 and 2). The role of bridging halides in the structure and magnetic properties of the complexes are investigated, and a possible magneto-structural correlation has been established. Influence of spin density of bridging halides on the magnitude of coupling constants has been discussed with the help of density functional theory (DFT) calculations.
Framework solids based on copper(II) halides (Cl/Br) and methylene-bridged bis-(1-hydroxybenzotriazole): synthesis, crystal structures, magneto-structural correlation, and density functional theory (DFT) studies / A., Sasmal; S., Shit; Rizzoli, Corrado; H., Wang; C., Desplanches; S., Mitra. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 51:(2012), pp. 10148-10157. [10.1021/ic300629v]
Framework solids based on copper(II) halides (Cl/Br) and methylene-bridged bis-(1-hydroxybenzotriazole): synthesis, crystal structures, magneto-structural correlation, and density functional theory (DFT) studies
RIZZOLI, Corrado;
2012-01-01
Abstract
A methylene-bridged 1-hydroxybenzotriazole derived ligand L [L = 1, 3-bis(benzotriazol-1-yl)-1,3-dioxapropane] has been synthesized and characterized by spectroscopic and structural methods. Reaction of L with two different copper(II) halides [CuX2; X = Br, Cl] in an identical condition yields two different compounds of similar compositions, {[Cu(μ-Br)(Br)(μ-L)]2}n·2nH2O (1) and {[Cu(μ-Cl)(Cl)(μ-L)]2}n·2nH2O (2), both being characterized by various physicochemical techniques. Single crystal X-ray studies reveal that they appear as 2D coordination polymers with similar bridging fashion of L. Low temperature magnetic susceptibility measurements reveal antiferromagnetic and ferromagnetic behaviors for 1 and 2 with magnetic coupling constants J = −15.2 and +1.7 cm–1, which are in a reasonable agreement with their calculated values (J = −9.79 and +0.68 cm–1 respectively, for 1 and 2). The role of bridging halides in the structure and magnetic properties of the complexes are investigated, and a possible magneto-structural correlation has been established. Influence of spin density of bridging halides on the magnitude of coupling constants has been discussed with the help of density functional theory (DFT) calculations.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.