Issue 39, 2023

Hybrid bronzes: mixed-valence organic–inorganic metal oxides as a tunable material platform

Abstract

We demonstrate that mixed-valence layered organic–inorganic metal oxides of the form (L)zHxMO3 (L = neutral ligand; M = Mo, W; z = 0.5, 1; 0 < x < 2), which we call hybrid bronzes, can be readily synthesized through mild solution-state self-assembly reactions to integrate the stability and electronic utility of inorganic metal oxide bronzes with the chemical diversity and functionality of organic molecules. We use single-crystal and powder X-ray diffraction coupled with X-ray, electronic, and vibrational spectroscopies to show that the products of aqueous pre-, mid-, or post-synthetic reduction are mixed-valence versions of highly crystalline layered hybrid oxides. Pillaring, bilayered, or canted bilayered arrangements of molecular arrays relative to inorganic sheets are dictated by judicious choice of organic ligands that can also incorporate chemical, redox, or photoactive handles. Significantly, bond-valence sum analysis and diffuse reflectance spectroscopy indicate relatively delocalized electronic behavior and four-point variable-temperature electrical transport measurements show that hybrid bronzes have comparable conductivity to their all-inorganic parent compounds. This work establishes a solution-processable, inexpensive, air- and water-stable, and non-toxic material family whose electronic bands can be readily tuned and doped, thereby positioning hybrid bronzes to address myriad material challenges.

Graphical abstract: Hybrid bronzes: mixed-valence organic–inorganic metal oxides as a tunable material platform

Supplementary files

Article information

Article type
Edge Article
Submitted
25 jul 2023
Accepted
12 sep 2023
First published
13 sep 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 10756-10767

Hybrid bronzes: mixed-valence organic–inorganic metal oxides as a tunable material platform

W. L. N. Dayaratne, R. Torres-Cadena, B. P. Schmitt, E. M. Westrick and A. Jaffe, Chem. Sci., 2023, 14, 10756 DOI: 10.1039/D3SC03828A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements