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Concurrent Enhancement of Thermopower and Conductivity via Modulation of Diacetylide-Electrode Coupling in Molecular
Jiung Jang1, Yuya Tanaka2, Danbi Lee3
1Department of Chemistry, Korea University, Seoul 02841, Republic of Korea.
Abstract:
The study of molecular thermoelectricity offers fundamental insights into charge transport via tunneling through organic and organometallic systems, with implications for nanoscale energy conversion technologies. Here, we investigate how molecule-electrode coupling strength influences thermoelectric performance in molecular junctions incorporating self-assembled monolayers of π-extended Ru(dppe)2-diacetylide complex. Surface modification of gold electrode with monatomic Pt and Pd layers via underpotential deposition enabled precise tuning of the strength of molecule-electrode contact. This tuning enhanced electronic interaction with the remotely positioned Ru core, promoted cumulene-like π-delocalization along the molecular backbone, reorganized frontier orbitals, and simultaneously enhanced the Seebeck coefficient and electrical conductivity to amplify the power factor by up to 111-fold compared to unmodified junctions. These findings highlight the broader potential of diacetylide complex to translate subtle orbital interactions into significant energy-conversion functions.
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