Journal of the American Chemical Society· 2026Q1
Solid–Liquid Transitions in 1D Metal–Organic Chalcogenolates
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- Q1SCImago
- 2026year
Short summary
Silver secondary-alkanethiolate 1D metal-organic chalcogenolates (MOChas) exhibit reversible solid-to-liquid phase transitions between 67–184 °C, a breakthrough for melt-processability in emerging hybrid materials.
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Key points
- Reversible solid-to-liquid phase transitions observed in 1D silver secondary-alkanethiolate MOChas at 67–184 °C.
- Ligand conformational flexibility and network structure contribute to low melting temperatures and enthalpy of fusion.
- Small-molecule serial femtosecond crystallography reveals 1D wire crystal motif.
- Green-yellow photoluminescence present in solid state, disappearing upon melting.
- Chiral domain unmixing observed in racemic crystals without affecting the inorganic network.
AI-generated from the title and abstract; the full text is not read.
Abstract
Abstract A lack of melt processability is noted for emerging hybrid material systems like metal–organic frameworks, lead-halide perovskites, and metal–organic chalcogenolates (MOChas). Here, we report reversible solid-to-liquid phase transitions ranging from 67 to 184 °C in silver secondary-alkanethiolate 1-dimensional (1D) MOChas. These MOChas were synthesized using five different secondary alkanethiols: 2-propanethiol, 2-butanethiol, 2-pentanethiol, 3-hexanethiol, and 4-heptanethiol. Structural characterization using small-molecule serial femtosecond crystallography (smSFX) reveals a 1D wire crystal motif. These 1D wire lattices exhibit green-yellow photoluminescence that disappears upon melting. The low melting temperature is attributed to the conformational flexibility of the secondary alkanethiol ligands, providing entropic benefits for the amorphous state. Furthermore, the transition from a nonmolecular, infinite covalent (Ag-SR)∞ network in the solid state to oligomolecular species (Ag-SR)x in the molten state contributes to a higher enthalpy of fusion. Large crystallites are observed to evolve from the liquid near the phase transition temperature. Notably, unmixing of chiral domains occurs in the racemic crystals while the inorganic network remains unchanged.
The authors' abstract, as published at the source. Journal of the American Chemical Society, 2026 · DOI ↗
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Field: Inorganic Chemistry
Inorganic ChemistryChemistry