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As the magnitude of the charge-transfer induced interfacial potential steps is proportional to the distance over which charge is transferred and inversely proportional to the lateral area (i.e., the footprint of the molecule) exceptions are found for (a) very short molecular wires23,39-45 and (b) for laterally extended molecules lying flat on a metal surface.47-50 Substantial electron back-transfer between metal and chemical anchoring groups on the molecule is often observed in these cases, which further allows shifting the frontier MOs into/through EF with only minor charging of the molecule.45,50
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As the magnitude of the charge-transfer induced interfacial potential steps is proportional to the distance over which charge is transferred and inversely proportional to the lateral area (i.e., the "footprint" of the molecule) exceptions are found for (a) very short molecular wires23,39-45 and (b) for laterally extended molecules lying flat on a metal surface.47-50 Substantial electron back-transfer between metal and chemical anchoring groups on the molecule is often observed in these cases, which further allows shifting the frontier MOs into/through EF with only minor charging of the molecule.45,50
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That the current through the neutral radicals reaches twice the value for the intrinsic molecule above the threshold voltage in the latter (V >1.2 V) can be attributed to the fact that in both N- and B-doped species, a second transport channel becomes available immediately after the SOMO itself double peaks in Figures 3b and 5 around EF
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That the current through the neutral radicals reaches twice the value for the intrinsic molecule above the threshold voltage in the latter (V >1.2 V) can be attributed to the fact that in both N- and B-doped species, a second transport channel becomes available immediately after the SOMO itself (double peaks in Figures 3b and 5 around EF).
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84869350904
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The molecular gap is slightly reduced (from ∼2.4 eV to ∼2.2 eV which we attribute to stabilization of the partially occupied LUMO (N-doping) and to destabilization of the partially occupied HOMO (B-doping).
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The molecular gap is slightly reduced (from ∼2.4 eV to ∼2.2 eV which we attribute to stabilization of the partially occupied LUMO (N-doping) and to destabilization of the partially occupied HOMO (B-doping).
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In ref 17, the ferrocene moiety is linked to the electrodes via extended π-conjugated segments. Each of the two organic ligands (linker unit with corresponding cyclopentadienyl ring) is a neutral radical by itself. As their mutual coupling through the central iron atom is reduced in this scenario, they separately align their SOMO to the Fermi level of the respective electrode. Consequently, a conductance peak is found around EF also for a formally closed-shell molecular wire
-
In ref 17, the ferrocene moiety is linked to the electrodes via extended π-conjugated segments. Each of the two organic ligands (linker unit with corresponding cyclopentadienyl ring) is a neutral radical by itself. As their mutual coupling through the central iron atom is reduced in this scenario, they separately align their SOMO to the Fermi level of the respective electrode. Consequently, a conductance peak is found around EF also for a formally closed-shell molecular wire.
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