Work

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

Year: 2026

Type: preprint

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.

Source: ChemRxiv

DOI: 10.26434/chemrxiv.15008200/v1

Authors: Jianwei Liang, Zhenhua Zhu, Haiquan Tian, Pengxiang Fu, Haixiang Han, Akseli Mansikkamäki, Shang-Da Jiang, Jinkui Tang, Zheng Zhou

Institutions: Tongji University, Beijing Institute of Technology, Liaocheng University, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, University of Oulu, Quantum Science Center of Guangdong-Hong Kong-Macao Greater Bay Area

Language: English

Topic: Magnetism in coordination complexes

Subfield: Electronic, Optical and Magnetic Materials

Field: Materials Science

Domain: Physical Sciences

Open Access status: green

Funders: National Natural Science Foundation of China, Tongji University, Fundamental Research Funds for the Central Universities

Award: G3300117461

OpenAlex ID: W7205014524

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