Steering Single-Electron Metal-Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages.

Metal complexes bearing single-electron metal-metal bonds (SEMBs) exhibit unusual electronic structures evoking strong magnetic coupling, and such bonds can be stabilized in the form of dimetallofullerenes (di-EMFs) in which two metals are confined in a carbon cage. Up to now, only a few di-EMFs containing SEMBs are reported, which are all based on a high-symmetry icosahedral ( I h ) C80 cage embedding homonuclear rare-earth bimetals, and a chemical modification of the I h -C80 cage is required to stabilize the SEMB. Herein, by introducing 3d-block transition metal titanium (Ti) along with 4f-block lanthanum (La) into the carbon cage, we synthesized the first crystallographically characterized SEMB-containing 3d-4f heteronuclear di-EMFs based on pristine fullerene cages. Four novel La-Ti heteronuclear di-EMFs were isolated, namely, LaTi@ D 3 h (5)-C78 , LaTi@ I h (7)-C80 , LaTi@ D 5 h (6)-C80 , and LaTi@ C 2 v (9)-C82 , and their molecular structures were unambiguously determined by single-crystal X-ray diffraction. Upon increasing the cage size from C78 to C82 , the La-Ti distance decreases from 4.31 to 3.97 Å, affording fine-tuning of the metal-metal bonding and hyperfine coupling, as evidenced by an electron spin resonance (ESR) spectroscopic study. Density functional theory (DFT) calculations confirm the existence of SEMB in all four LaTi@C2 n di-EMFs, and the accumulation of electron density between La and Ti atoms shifts gradually from the proximity of the Ti atom inside C78 to the center of the LaTi bimetal inside C82 due to the decrease of the La-Ti distance. The electronic properties of LaTi@C2 n heteronuclear dimetallofullerenes differ apparently from their homonuclear La2 @C2 n counterparts, revealing the peculiarity of heteronuclear dimetallofullerenes with the involvement of 3d-block transition metal Ti.