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PreprintCC BYChemRxiv

A tetrahedral four-center–one-electron lanthanide–lanthanide bond

  • Jianwei Liang1,2
  • Zhenhua Zhu3,4
  • Haiquan Tian5,6
  • Pengxiang Fu7,8
  • Haixiang Han1,2
  • Akseli Mansikkamäki9,10
  • Shang-Da Jiang7,8,11
  • Jinkui Tang3,4
  • Zheng Zhou1,2
11 affiliations
  1. 1School of Materials Science and Engineering
  2. 2Tongji University
  3. 3School of Chemistry and Chemical Engineering
  4. 4Beijing Institute of Technology
  5. 5Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Energy Science and Technology
  6. 6Liaocheng University
  7. 7Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, State Key Laboratory of Luminescent Materials and Devices
  8. 8South China University of Technology
  9. 9NMR Research Unit
  10. 10University of Oulu
  11. 11Quantum Science Center of Guangdong
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Abstract

Direct lanthanide–lanthanide bonding has been so far established only in two- and threecenter systems. Here we report lanthanide complexes containing a tetrahedral Ln4 core featuring a four-center–one-electron (4c–1e) lanthanide–lanthanide bond. In a two-step reductive assembly, six-electron reduction of hexaphenylbenzene (HPB) generates a geometrically reorganized HPB6– framework that provides a multimetal-binding environment for assembly of a core comprising four LnII centers and one additional electron. Structural, spectroscopic, magnetic, and computational analyses show that this electron occupies a diffuse cluster orbital of mixed Ln 6s/6p/5d character and is delocalized over the four central metal centers. These results establish a three-dimensional regime of single-electron Ln–Ln bonding and demonstrate how deeply reduced molecular carbon frameworks can access unconventional f-element electronic structures.

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Cite

BibTeXRIS
BibTeX
@misc{liang2026tetrahedral,
  title = {{A tetrahedral four-center–one-electron lanthanide–lanthanide bond}},
  author = {Jianwei Liang and Zhenhua Zhu and Haiquan Tian and Pengxiang Fu and Haixiang Han and Akseli Mansikkamäki and Shang-Da Jiang and Jinkui Tang and Zheng Zhou},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008200/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008200/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - A tetrahedral four-center–one-electron lanthanide–lanthanide bond
AU  - Jianwei Liang
AU  - Zhenhua Zhu
AU  - Haiquan Tian
AU  - Pengxiang Fu
AU  - Haixiang Han
AU  - Akseli Mansikkamäki
AU  - Shang-Da Jiang
AU  - Jinkui Tang
AU  - Zheng Zhou
PY  - 2026
DA  - 2026/09/02
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008200/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008200/v1
AB  - Direct lanthanide–lanthanide bonding has been so far established only in two- and threecenter systems. Here we report lanthanide complexes containing a tetrahedral Ln4 core featuring a four-center–one-electron (4c–1e) lanthanide–lanthanide bond. In a two-step reductive assembly, six-electron reduction of hexaphenylbenzene (HPB) generates a geometrically reorganized HPB6– framework that provides a multimetal-binding environment for assembly of a core comprising four LnII centers and one additional electron. Structural, spectroscopic, magnetic, and computational analyses show that this electron occupies a diffuse cluster orbital of mixed Ln 6s/6p/5d character and is delocalized over the four central metal centers. These results establish a three-dimensional regime of single-electron Ln–Ln bonding and demonstrate how deeply reduced molecular carbon frameworks can access unconventional f-element electronic structures.
ER  -