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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - The Conductance and Thermopower Behavior of Pendent Trans-Coordinated Palladium(II) Complexes in Single-Molecule Junctions
AU - Bastante, P.
AU - Davidson, R.J.
AU - Al Malki, W.
AU - Salthouse, R.J.
AU - Cea, P.
AU - Martin, S.
AU - Batsanov, A.S.
AU - Lambert, C.J.
AU - Bryce, M.R.
AU - Agrait, N.
N1 - Export Date: 5 September 2024
PY - 2024/9/10
Y1 - 2024/9/10
N2 - The present work provides insight into the effect of connectivity within isomeric 1,2-bis(2-pyridylethynyl)benzene (bpb) palladium complexes on their electron transmission properties within gold|single-molecule|gold junctions. The ligands 2,2′-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(4-(methylthio)pyridine) (Lm) and 6,6′-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(3-(methylthio)pyridine) (Lp) were synthesized and coordinated with PdCl2 to give the trans-Pd(Lm or p)Cl2 complexes. X-ray photoelectron spectroscopy (XPS) measurements shed light on the contacting modes of the molecules in the junctions. A combination of scanning tunneling microscopy–break junction (STM–BJ) measurements and density functional theory (DFT) calculations demonstrate that the typical lower conductance of meta- compared with para-connected isomers in a molecular junction was suppressed upon metal coordination. Simultaneously there was a modest increase in both conductance and Seebeck coefficient due to the contraction of the HOMO–LUMO gap upon metal coordination. It is shown that the low Seebeck coefficient is primarily a consequence of how the resonances shift relative to the Fermi energy.
AB - The present work provides insight into the effect of connectivity within isomeric 1,2-bis(2-pyridylethynyl)benzene (bpb) palladium complexes on their electron transmission properties within gold|single-molecule|gold junctions. The ligands 2,2′-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(4-(methylthio)pyridine) (Lm) and 6,6′-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(3-(methylthio)pyridine) (Lp) were synthesized and coordinated with PdCl2 to give the trans-Pd(Lm or p)Cl2 complexes. X-ray photoelectron spectroscopy (XPS) measurements shed light on the contacting modes of the molecules in the junctions. A combination of scanning tunneling microscopy–break junction (STM–BJ) measurements and density functional theory (DFT) calculations demonstrate that the typical lower conductance of meta- compared with para-connected isomers in a molecular junction was suppressed upon metal coordination. Simultaneously there was a modest increase in both conductance and Seebeck coefficient due to the contraction of the HOMO–LUMO gap upon metal coordination. It is shown that the low Seebeck coefficient is primarily a consequence of how the resonances shift relative to the Fermi energy.
U2 - 10.1021/acsomega.4c06475
DO - 10.1021/acsomega.4c06475
M3 - Journal article
C2 - 39281963
VL - 9
SP - 38303
EP - 38312
JO - ACS Omega
JF - ACS Omega
SN - 2470-1343
IS - 36
ER -