Influence of the bridging coordination of DMSO on the exchange interaction character in the binuclear copper(II) complex with the nonsymmetrical exchange fragment

Abstract

The binuclear copper(II) complex [Cu 2 L(CH 3 COO)] (I), where L 3-is the azomethine trianion based on 3 methyl 4 formyl 1 phenylpyrazol 5 one and 1,3 diaminopropan 2 ol, and its DMSO adduct (II) in which the DMSO molecule acts as an additional bridging ligand are synthesized. The structure of com plex II is determined by X ray diffraction analysis, and the structure parameters of the coordination unit of complex I are determined by EXAFS spectroscopy. The µ 2 coordination of the DMSO molecule in com pound II results in a change in the sign of the exchange interaction parameter. In complex I, the antiferro magnetic exchange interaction (2J = -169 cm -1 ) occurs between the copper(II) ions. The exchange inter action of the ferromagnetic type (2J = 174 cm -1 ) is observed in complex II. The quantum chemical calcula tions of the magnetic exchange parameters by the density functional theory method show that the role of the DMSO molecule as a switch of the exchange interaction character is exclusively the stabilization of the "bro ken" conformation of the metallocycles.

Solvothermal Synthesis of [Cr7S8(en)8Cl2]Cl3 ⋅ 2H2O with Magnetically Frustrated [Cr7S8]5+ Double‐Cubes**

“…Apart from this, Kogan et al. investigated its applicability as a bridging ligand to facilitate exchange interactions between transition metal centers in binuclear complexes [48] . However, employing DMSO as a potential sulfur source is rare in solution chemistry.…”

“…[46,47] Apart from this, Kogan et al investigated its applicability as a bridging ligand to facilitate exchange interactions between transition metal centers in binuclear complexes. [48] However, employing DMSO as a potential sulfur source is rare in solution chemistry. About a decade ago, Li et al synthesized an organic intercalated iron sulfide layered semiconductor using DMSO as a starting material without using elemental sulfur or thiourea.…”

Dimethyl sulfoxide as a strongly coordinating solvent: 3′,4′-dihydroxyflavone-Cu(II)-DMSO system case study

“…The DMSO-H 2 O binary mixture (Sergievskii, Skorobogat'Ko, and Rudakov, 2010;Roy et al, 2011) is a common solvent in experiments involving cell cultures since a small amount of DMSO is well tolerated and does not change the culture viability (Allen et al, 2008;Singh and Ghosh, 2016). In addition, DMSO is well known as a strongly coordinating solvent (Levchenkov et al, 2014;Rancan and Armelao, 2015;Rancan et al, 2019;Patra et al, 2013) . Highly polarized S=O double bond has positive and negative charges localized on sulfur and oxygen atoms, respectively (Cioslowski and Surján, 1992).…”

Synthesis, characterization and crystal structures of Ni(II) and Cu(I) complexes with the condensation product of 2-(diphenylphosphino)benzaldehyde and 1-hydrazinophthalazine

“…1-Hydrazinophthalazine hydrazones of mono-and dicarbonyl compounds are versatile chelating agents due to their conformational flexibility, possibility of tautomerism and coordination in either the neutral or anionic form [2][3][4][5][6][7][8][9][10][11]. Also, in some of the reported binuclear metal complexes with these ligands, the phthalazine ring act as an NN′ donor bridge between the two metal centers [7,8,[12][13][14][15][16]]. Researcher's interest for metal complexes with 1-hydrazinophthalazine hydrazone ligands is mainly associated with their magnetic properties [6][7][8][12][13][14][15][16] and biological activity [3][4][5].…”

“…Also, in some of the reported binuclear metal complexes with these ligands, the phthalazine ring act as an NN′ donor bridge between the two metal centers [7,8,[12][13][14][15][16]]. Researcher's interest for metal complexes with 1-hydrazinophthalazine hydrazone ligands is mainly associated with their magnetic properties [6][7][8][12][13][14][15][16] and biological activity [3][4][5]. Hydrazone ligands derived from 2-(diphenylphosphino)benzaldehyde, which contain significantly different types of "hard" and "soft" donor atoms, have attracted considerable attention due to their interesting coordination properties [17][18][19], catalytic [20][21][22][23] and biological activity [24][25][26].…”