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 Jūl. 2023
Accepted
12 Sept. 2023
First published
13 Sept. 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

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