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 ) C 80 cage embedding homonuclear rare-earth bimetals, and a chemical modification of the I h -C 80 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)-C 78 , LaTi@ I h (7)-C 80 , LaTi@ D 5 h (6)-C 80 , and LaTi@ C 2 v (9)-C 82 , and their molecular structures were unambiguously determined by single-crystal X-ray diffraction. Upon increasing the cage size from C 78 to C 82 , 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@C 2 n di-EMFs, and the accumulation of electron density between La and Ti atoms shifts gradually from the proximity of the Ti atom inside C 78 to the center of the LaTi bimetal inside C 82 due to the decrease of the La-Ti distance. The electronic properties of LaTi@C 2 n heteronuclear dimetallofullerenes differ apparently from their homonuclear La 2 @C 2 n counterparts, revealing the peculiarity of heteronuclear dimetallofullerenes with the involvement of 3d-block transition metal Ti.