As global temperatures increase due to climate change, the accumulation of excess heat on Earth presents a valuable resource that can be harnessed for electricity generation using thermoelectric materials. However, the intricate structures of bulk thermoelectric materials pose significant challenges to their comprehensive understanding and limit performance. Additionally, their relatively high production costs present practical obstacles. A promising solution to these issues lies in molecular control and the use of molecular junctions. Molecules are predicted to surpass the performance of existing bulk materials in energy conversion because they can be chemically tuned to achieve high thermoelectric efficiencies. This review identifies the thermoelectric parameters that affect the performance of molecular junctions. It also explores various experimental platforms for measuring thermoelectric performance from single molecules to assemblies of hundreds of molecules. Finally, it highlights recent advancements in thermoelectric molecular junctions, focusing on the crucial roles of electrodes and metal components within the molecules, such as Ru complexes, metalloporphyrins, metallocenes, conjugated silane wires, and endohedral metallofullerenes. Ultimately, our review provides a comprehensive analysis of strategies to enhance the thermoelectric efficiency of molecular junctions.
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