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Updated: Aug 9, 2025
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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
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Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone
Hadi Hachem1, HengBo Cui2, Reizo Kato2
1Institut des Sciences Chimiques de Rennes, Université de Rennes, CNRS, UMR 6226, F-35000 Rennes, France.
Inorganic Chemistry
|February 24, 2023
Summary
New nickel diselenolene complexes exhibit unique mixed-valence, multi-component conducting salts. These materials show semiconducting or quasi-metallic properties, offering rare insights into nickel-based conductive materials.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Solid-State Physics
Background:
- Nickel bis(diselenolene) complexes are explored for conductive properties.
- Mixed-valence compounds offer unique electronic characteristics.
- Existing nickel diselenolene mixed-valence salts are scarce.
Purpose of the Study:
- To synthesize and characterize novel mixed-valence, multi-component nickel bis(diselenolene) salts.
- To investigate the influence of counter ions on salt stoichiometry and structure.
- To determine the electronic properties (semiconducting/metallic) of these new materials.
Main Methods:
- Electrocrystallization of monoanionic nickel bis(diselenolene) species.
- Varying counter ions (Et4N+, nBu4N+, Ph4P+) to control stoichiometry.
- High-pressure transport measurements (up to 10 GPa).
- Band structure calculations.
Main Results:
- Successfully synthesized 1:2 and 1:3 nickel bis(diselenolene) salts with different counter ions.
- Observed highly dimerized/trimerized bimetallic/trimetallic units.
- Determined semiconducting behavior for [Ph4P][Ni(Me-thiazds)2]3.
- Identified quasi-metallic behavior for [Et4N][Ni(Me-thiazds)2]2 and [NBu4][Ni(Me-thiazds)2]2 salts.
Conclusions:
- These findings present rare examples of mixed-valence conducting nickel diselenolene salts.
- The counter ion significantly impacts the stoichiometry and structural assembly.
- The synthesized salts exhibit tunable electronic properties, ranging from semiconducting to quasi-metallic.
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