Electrode–molecule coupling dictates charge transport in rhenium(i)-based organometallic single-molecule junctions
Journal of Materials Chemistry C, 2026 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Basım Tarihi: 2026
- Doi Numarası: 10.1039/d6tc00423g
- Dergi Adı: Journal of Materials Chemistry C
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, Compendex, INSPEC, MEDLINE
- Sivas Cumhuriyet Üniversitesi Adresli: Evet
Özet
Understanding charge transport through single-molecule junctions (SMJs) is pivotal to molecular electronics (ME) as it provides fundamental insights into electron transport at the ultimate limit of device miniaturization. While Pt-, Ru-, and Fe-based organometallic complexes have been widely studied, Re(i) carbonyl complexes remain underexplored in ME, despite their intriguing photophysical and light-emitting applications. In this work, a theoretical model study on the electrical (current–voltage) characteristics of two distinct Re(i) carbonyl complexes bearing Re-P and Re-N,N linkages in a two-terminal device with a vertical configuration, Au/Re(i)-complex/Au SMJs, was meticulously performed. Coherent tunneling and thermally activated hopping are described using the Landauer formalism and Marcus theory, respectively. Variations in molecular architecture led to pronounced differences in electrical features, transport parameters, and thus the underlying mechanisms. The influence of key physical parameters, including electrical dipole moment, electrode–molecule coupling, voltage division factor, and temperature, on the current–voltage (I–V) characteristics is systematically analyzed to understand charge transport in SMJs. Electrical current rectification in the tris(4-mercaptophenyl) phosphine and phenanthroline-linked Re complex junctions shows dependence on the alignment of frontier molecular orbitals to the Fermi level of electrodes, reorganization energy, applied bias, electrode coupling, and temperature. This study provides an original framework for designing redox-active, organometallic single-molecule junctions and understanding charge transport at the molecular level.