Mesoxalate as Cu(ii)–Ln(iii) linker in the construction of MOFs in DMSO/water medium

Abstract

Fivenew heterometallic 3d-4f metal-organic frameworks with the general formula ijLnIJH 2 O) z Cu 3 IJHmesox) 3 DMSO]·xH 2 O·yDMSO IJLnIJIII) = La, Ce, Pr, Nd and Eu; H 4 mesox = mesoxalic or dihydroxymalonic acid; and DMSO = dimethylsulfoxide) have been prepared by crystal growth in agarose gel in a mixed solvent (DMSO/water) medium. LaCu 3 , CeCu 3 , PrCu 3 and NdCu 3 yield prismatic wellformed chiral crystals, whereas EuCu 3 produces laminar and badly-shaped crystals. The structural analysis shows cubic neutral chiral (10,3)-a networks for the former four compounds. On the other hand, EuCu 3 yields neutral chains with lower connectivity, crystallizing in a monoclinic space group. The magnetic susceptibility study reveals antiferromagnetic coupling among the copperIJII) ions through the mesoxalatealkoxo exchange pathway. Theoretical DFT studies agree with the magnetic susceptibility investigations and show a correlation between the intensity of the magnetic coupling and the bridging Cu-O-Cu angles. CrystEngComm This journal isScheme 1 (a) Mesoxalic acid (H 4 mesox). (b) ijCu 3 IJHmesox) 3 ] 3− unit.

Metal‐organic Frameworks Incorporating Multiple Metal Elements

“…[Ln(H 2 O) z Cu 3 (Hmesox) 3 DMSO] ⋅ xH 2 O ⋅ yDMSO materials (Ln(III)=La, Ce, Pr, Nd and Eu; H 4 mesox=dihydroxymalonic acid; and DMSO=dimethylsulfoxide) have been prepared by crystal growth in agarose gel in a mixed solvent (DMSO/water) medium. The magnetic susceptibility study performed for LaCu 3 revealed the occurrence of antiferromagnetically coupled Cu(II) equilateral triangles whose apical positions can also be occupied by water molecules . Tripuramallu et al .…”

Synthesis, structure and magnetic properties of a cobalt(II) mesoxalate 1D coordination polymer

“…In the last decade, we have studied the formation of coordination polymers with the mesoxalate ligand, the conjugated base of the mesoxalic acid (mesoxalic acid=2,2‐dihydroxyl‐propanedioic acid or 2,2‐dihydroxyl‐malonic acid, H 4 mesox) (Scheme 1). This ligand has six‐donor oxygens, four from the two carboxylate groups and two from the two hydroxyl groups, and it's complex formation has resulted in great structural diversity [1–10] …”

“…This ligand has six-donor oxygens, four from the two carboxylate groups and two from the two hydroxyl groups, and it's complex formation has resulted in great structural diversity. [1][2][3][4][5][6][7][8][9][10] In some of the complexes we have prepared such as (Ph 4 P)[MnCu 3 (Hmesox) 3 Cl] or [LaCu 3 (Hmesox) 3 (DMSO)], the mesoxalate ligand acted as Hmesox 3À giving the [Cu 3 (Hmesox) 3 X] 4À (X=Cl À and Br À ) and [Cu 3 (Hmesox) 3 Y] 3À (Y=H 2 O or DMSO) trinuclear copper(II) metalloligands. [5][6][7]9,10] Furthermore, it acted as H 2 mesox 2À when linked to Ln(III) in [Ln 2 (H 2 mesox) 6 ] • 6H 2 O compounds.…”

“…The study of the magnetic properties of those complexes revealed that the intensity of the coupling is related to the bridging mode of the mesoxalate ligand. Strong magnetic coupling is found for the Hmesox 3− compounds where the carboxylate and alkoxido bridges mediate the magnetic coupling [5–7,9,10] . On the other hand, weak magnetic coupling is found in the H 2 mesox 2− compounds where the magnetic coupling is mediated by a diol bridge [3,4] …”

“…[1][2][3][4][5][6][7][8][9][10] In some of the complexes we have prepared such as (Ph 4 P)[MnCu 3 (Hmesox) 3 Cl] or [LaCu 3 (Hmesox) 3 (DMSO)], the mesoxalate ligand acted as Hmesox 3À giving the [Cu 3 (Hmesox) 3 X] 4À (X=Cl À and Br À ) and [Cu 3 (Hmesox) 3 Y] 3À (Y=H 2 O or DMSO) trinuclear copper(II) metalloligands. [5][6][7]9,10] Furthermore, it acted as H 2 mesox 2À when linked to Ln(III) in [Ln 2 (H 2 mesox) 6 ] • 6H 2 O compounds. [3,4] We have found that the compounds formed exhibited from molecular to three-dimensional structures.…”