Steering Single-Electron Metal–Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages
Heteronuclear molecule
Superatom
Endohedral fullerene
Bimetal
Homonuclear molecule
DOI:
10.1021/jacs.3c07686
Publication Date:
2023-10-03T15:11:31Z
AUTHORS (9)
ABSTRACT
Metal complexes bearing single-electron metal-metal bonds (SEMBs) exhibit unusual electronic structures evoking strong magnetic coupling, and such can be stabilized in the form of dimetallofullerenes (di-EMFs) which two metals are confined a carbon cage. Up to now, only few di-EMFs containing SEMBs reported, all based on high-symmetry icosahedral (Ih) C80 cage embedding homonuclear rare-earth bimetals, chemical modification Ih-C80 is required stabilize SEMB. Herein, by introducing 3d-block transition metal titanium (Ti) along with 4f-block lanthanum (La) into cage, we synthesized first crystallographically characterized SEMB-containing 3d-4f heteronuclear pristine fullerene cages. Four novel La-Ti were isolated, namely, LaTi@D3h(5)-C78, LaTi@Ih(7)-C80, LaTi@D5h(6)-C80, LaTi@C2v(9)-C82, their molecular unambiguously determined single-crystal X-ray diffraction. Upon increasing size from C78 C82, distance decreases 4.31 3.97 Å, affording fine-tuning bonding hyperfine as evidenced an electron spin resonance (ESR) spectroscopic study. Density functional theory (DFT) calculations confirm existence SEMB four LaTi@C2n di-EMFs, accumulation density between La Ti atoms shifts gradually proximity atom inside center LaTi bimetal C82 due decrease distance. The properties differ apparently La2@C2n counterparts, revealing peculiarity involvement Ti.
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