# Ligand-Directed Valence Band Engineering in Pb<sup>2+</sup> Hybrid Crystals: Achieving Dispersive Bands and Shallow Valence Band Maximum

https://mdr.nims.go.jp/datasets/b08fcf8c-e0b3-4c24-9804-b2c2be9388ac

## File

- [Main_Text_fin_clean.pdf](https://mdr.nims.go.jp/filesets/5760007f-409e-4c86-80d5-34f465feb555/download) ([Detail](https://mdr.nims.go.jp/filesets/5760007f-409e-4c86-80d5-34f465feb555.md))

## Id

b08fcf8c-e0b3-4c24-9804-b2c2be9388ac

## Local identifier



## Visibility

open_to_public

## State

published

## Created at

2025-03-26T00:26:36.532142Z

## Updated at

2025-11-20T03:30:09.854463Z

## Published at

2025-11-19T23:30:16.643863Z

## Doi

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

## First published url

https://doi.org/10.1021/jacs.4c12804

## Date published

2024-12-11

## Recorded date published

2024-12-11

## Resource type

journal_article

## Manuscript type

accepted_manuscript

## Collection



## Title

- title: 'Ligand-Directed Valence Band Engineering in Pb<sup>2+</sup> Hybrid Crystals:
    Achieving Dispersive Bands and Shallow Valence Band Maximum'
  title_type: original
  lang: en

## Description

- description: 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.
  description_type: abstract
  lang: und

## Creator

- name: Daiki Umeyama
  role: author
  orcid: https://orcid.org/0000-0003-4773-4020
- name: Soshi Iimura
  role: author
  orcid: https://orcid.org/0000-0003-3270-155X

## Contact agent



## Publisher

organization: American Chemical Society (ACS)

## Managing organization



## Keyword

- subject: Valence Band Engineering
  schema: not_defined

## Rights

- description: 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.
  identifier: http://rightsstatements.org/vocab/InC/1.0/

## Other identifier(s)



## Data origin

- data_origin_type: other

## Embargo

start_date: 2024-11-20
end_date: 2025-11-20

## Journal

- title: Journal of the American Chemical Society
  issn: '00027863'
  volume: '146'
  issue: '49'
  start_page: 33964
  end_page: 33972

## Conference



## Related item



## Funding

- identifier: JP24K08460
  funder_name: Japan Society for the Promotion of Science
  description: 日本学術振興会
- identifier: " JP21H04612"
  funder_name: Japan Society for the Promotion of Science
  description: 日本学術振興会

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## Fileset

- id: 5760007f-409e-4c86-80d5-34f465feb555
  filename: Main_Text_fin_clean.pdf
  content_type: application/pdf
  size: 2482250
  md5: 26a9ae530f4dbef13286c2b12fa2f38e

## Thumbnail

fileset_id: 5760007f-409e-4c86-80d5-34f465feb555
filename: Main_Text_fin_clean.pdf