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While crystalline hybrid solids hold great potential as novel semiconductors, most semiconductive hybrids utilize transition metal ions, which inherently limit carrier mobility due to the small band dispersion derived from the d orbitals. The filled s orbitals of post-transition metal ions offer the potential to design dispersed valence bands, but a method to translate the local structure design of these metal ions to valence band engineering is still in development. This study focuses on Pb²⁺-containing hybrid crystals, developing a simple strategy to control Pb²⁺ coordination geometry through the molecular design of azole ligands. By pre-programming the coordination number of Pb²⁺ with azolate ligands, we succeeded in obtaining an isotropic coordination environment at a higher coordination number, resulting in a dispersed valence band and shallow valence band maximum while having a wide band gap. Detailed analysis of the band structures reveals that the energy levels and symmetry of the molecular orbitals of the anions play an important role in realizing these anti-nomic properties. This ligand-directed approach achieves both isotropy and covalency in the coordination bond by exploiting the diversity of molecular orbitals. Our findings provide a foundation for future design strategies to optimize electronic structures in hybrid materials, advancing their application in semiconductive devices.

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  This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.4c12804.

Keyword: Valence Band Engineering

Date published: 2024-12-11

Publisher: American Chemical Society (ACS)

Journal:

• Journal of the American Chemical Society (ISSN: 00027863) vol. 146 issue. 49 p. 33964-33972

Funding:

• Japan Society for the Promotion of Science JP24K08460 (日本学術振興会)
• Japan Society for the Promotion of Science JP21H04612 (日本学術振興会)

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.5384

First published URL: https://doi.org/10.1021/jacs.4c12804

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Updated at: 2025-11-20 12:30:09 +0900

Published on MDR: 2025-11-20 08:30:16 +0900