Multifunctional Copper(I) Coordination Polymers with Aromatic Mono- and Ditopic Thioamides

Area of Science:

• Coordination Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Copper halides (CuX) are versatile precursors for coordination chemistry.
• Thiobenzamide (TBA) and 1,4-dithiobenzamide (DTBA) are organic ligands with potential coordinating abilities.
• Coordination polymers (CPs) and molecular complexes offer diverse structural motifs and properties.

Purpose of the Study:

• To synthesize and characterize novel coordination polymers and molecular complexes using copper halides and thiobenzamide derivatives.
• To investigate the structural diversity and properties of the resulting copper-iodide and copper-bromide compounds.
• To explore the potential applications of these materials in sensing technologies.

Main Methods:

• Direct reactions of copper halides (CuBr, CuI) with thiobenzamide (TBA) and 1,4-dithiobenzamide (DTBA) under ambient conditions.
• Isolation and characterization of one-dimensional (1D) and two-dimensional (2D) coordination polymers, as well as molecular complexes.
• Recrystallization techniques to obtain solvated species.
• Investigation of luminescence and electrical semiconductivity properties.
• Theoretical calculations to rationalize observed electronic properties.

Main Results:

• Formation of 1D CPs ([CuI(TBA)]n, [Cu3I3(TBA)2]n, [CuBr(TBA)]n) and molecular complexes ([CuI(TBA)3], [Cu2I2(TBA)4]·2MeCN).
• Isolation of isostructural 1D CP solvated species ([CuI(TBA)·S]n, [CuBr(TBA)·S]n) and 2D CPs ([CuI(DTBA)·S]n).
• Observed variable luminescence and electrical semiconductivity in solvated 1D CPs (1·S and 5·S) dependent on solvent molecules.
• Demonstrated potential for sensing volatile organic vapors through significant changes in emission upon solvent exposure.

Conclusions:

• The reaction conditions and ligand choice influence the formation of diverse copper coordination architectures.
• Solvated coordination polymers exhibit tunable photophysical and electronic properties.
• These materials show promise for developing naked-eye sensors for volatile organic vapors.
• Theoretical studies support the understanding of their electronic behavior.