Axial ligands of Ru2 tuning Zn2 + rearrangement to form a new heterometallic carbonate: Synthesis, structure and magnetic properties

• Ru2(CO3)43 − units are linked by tetrahedral Zn2 + forms layer {ZnHRu2(CO3)4(H2O)2}n.
• The axial position ligands (H2O or Cl−) of Ru2 account for the Zn environments.
• Fitting results on the data of M vs H and χMT vs T are in agreement very well.

The self-assembly of Ru2(CO3)43−  and Zn2 + in neutral aqueous solution forms heterometallic carbonate ZnHRu2(CO3)4(H2O)2·2H2O (1). X-ray crystallographic analysis and magnetic investigation show that 1 behaves as 2D antiferromagnetic layers. It is different from those light transitional metal d1–9 centers (Mn, Co, and Ni), which merely exhibit octahedral MO6 environment and trans- or cis-mode link Ru2 dimers to form 2D and 3D frameworks, the production of 1 shows Zn2 + adopting tetrahedral environment. Compared with Zn2 + adopting octahedral environment in KZn(H2O)6[Zn(H2O)2Ru2(CO3)4Cl2]·4H2O, it proves that the axial position ligands (L) of Ru2 dimers account for the tetrahedral ZnO4 (L = H2O) or octahedral ZnO6 (L = Cl−) environments, and this is also due to the d10 electronic configuration of Zn2 + with the equivalent crystal field energy of the tetrahedral ZnO4 and octahedral ZnO6 symmetry.

Ru2(CO3)43− units are linked by tetrahedral Zn2 + forming heterometallic layer of {ZnHRu2(CO3)4(H2O)2}n, and it proves that the axial position ligands (L) of Ru2 dimer account for the tetrahedral ZnO4 (L = H2O) or octahedral ZnO6 (L = Cl−) environments.Figure optionsDownload as PowerPoint slide