Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding

Magnetic effects of lanthanide bonding Lanthanide coordination compounds have attracted attention for their persistent magnetic properties near liquid nitrogen temperature, well above alternative molecular magnets. Gould et al . report that introducing metal-metal bonding can enhance coercivity. Reduction of iodide-bridged terbium or dysprosium dimers resulted in a single electron bond between the metals, which enforced alignment of the other valence electrons. The resultant coercive fields exceeded 14 tesla below 50 and 60 kelvin for the terbium and dysprosium compounds, respectively. —JSY

Application of Density Functional Theory in Coordination Chemistry: A Case Study of Group 13 Monohalide as a Ligand

The chemistry of Group 13 Monohalide is of great interest due to its isoelectronic relationship with carbon monoxide and dinitrogen. In recent years, theoretical and experimental studies have been evolved on the group-13 atom-based diatomic molecules as a ligand. The synthetic, characterisation and reactivity of various metal complexes have been well discussed in recent reviews. The nature of the metal bonding of these ligands of various types has been explained in addition by the variety of theoretical studies (using DFT methods) such as FMO and EDA. This chapter has a comprehensive experimental and theoretical study of group 13 monohalides as a ligand in coordination chemistry.

Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn2Sb5]3−

Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. Here we report the synthesis, experimental, and theoretical characterizations of four ternary clusters ([M2(CO)6Sn2Sb5]3− (M = Cr, Mo), and [(MSn2Sb5)2]4−, (M = Cu, Ag)) in the process of capturing the hypho- [Sn2Sb5]3− in ethylenediamine (en) solution. We show that the coordination of the binary anion to transition-metal ions or fragments provides additional stabilization due to the formation of locally σ-aromatic units, producing a spherical aromatic shielding region in the cages. While in the case of [Mo2(CO)6Sn2Sb5]3− stabilization arises from locally σ-aromatic three-centre and five-centre two-electron bonds, aromatic islands in [(AgSn2Sb5)2]4− and [(CuSn2Sb5)2]4− render them globally antiaromatic. This work describes the coordination chemistry of the versatile building block [Sn2Sb5]3−, thus providing conceptual advances in the field of metal-metal bonding in clusters.