To explore solvent gating of single-molecule electrical conductance due to solvent-molecule interactions, charge transport through single-molecule junctions with different anchoring groups in various solvent environme...To explore solvent gating of single-molecule electrical conductance due to solvent-molecule interactions, charge transport through single-molecule junctions with different anchoring groups in various solvent environments was measured by using the mechanically controllable break junction technique. We found that the conductance of single-molecule junctions can be tuned by nearly an order of magnitude by varying the polarity of solvent. Furthermore, gating efficiency due to solvent–molecule interactions was found to be dependent on the choice of the anchor group. Theoretical calculations revealed that the polar solvent shifted the molecular-orbital energies, based on the coupling strength of the anchor groups. For weakly coupled molecular junctions, the polar solvent–molecule interaction was observed to reduce the energy gap between the molecular orbital and the Fermi level of the electrode and shifted the molecular orbitals. This resulted in a more significant gating effect than that of the strongly coupled molecules. This study suggested that solvent–molecule interaction can significantly affect the charge transport through single-molecule junctions.展开更多
The emergence of molecular spintronics offers a unique chance for the design of molecular devices with different spin-states,and the control of spin-state becomes essential for molecular spin switches.However,the intr...The emergence of molecular spintronics offers a unique chance for the design of molecular devices with different spin-states,and the control of spin-state becomes essential for molecular spin switches.However,the intrinsic spin switching from low-to high-spin state is a temperature-dependent process with a small energy barrier where low temperature is required to maintain the low-spin state.Thus,the room-temperature operation of single-molecule devices has not yet been achieved.Herein,we present a reversible single-molecule conductance switch by manipulating the spin states of the molecule at room temperature using the scanning tunneling microscope break-junction(STM-BJ)technique.The manipulation of the spin states between S=0 and S=1 is achieved by complexing or decomplexing the pyridine derivative molecule with a square planar nickel(Ⅱ)porphyrin.The bias-dependent conductance evolution proves that the strong electric field between the nanoelectrodes plays a crucial role in the coordination reaction.The density functional theory(DFT)calculations further reveal that the conductance changes come from the geometric changes of the porphyrin ring and spin-state switching of the Ni(Ⅱ)ion.Our work provides a new avenue to investigate room-temperature spin-related sensors and molecular spintronics.展开更多
基金This work was supported by National Key R&D Project of China(2017YFA0204902)National Natural Science Foundation of China(21722305,21673195,21973079)+2 种基金FET Open project 767187–Qu IETthe EU project BAC-TO-FUELthe UK EPSRC grants EP/N017188/1,EP/P027156/1 and EP/N03337X/1
文摘To explore solvent gating of single-molecule electrical conductance due to solvent-molecule interactions, charge transport through single-molecule junctions with different anchoring groups in various solvent environments was measured by using the mechanically controllable break junction technique. We found that the conductance of single-molecule junctions can be tuned by nearly an order of magnitude by varying the polarity of solvent. Furthermore, gating efficiency due to solvent–molecule interactions was found to be dependent on the choice of the anchor group. Theoretical calculations revealed that the polar solvent shifted the molecular-orbital energies, based on the coupling strength of the anchor groups. For weakly coupled molecular junctions, the polar solvent–molecule interaction was observed to reduce the energy gap between the molecular orbital and the Fermi level of the electrode and shifted the molecular orbitals. This resulted in a more significant gating effect than that of the strongly coupled molecules. This study suggested that solvent–molecule interaction can significantly affect the charge transport through single-molecule junctions.
基金supported by the National Natural Science Foundation of China(nos.21673195,21722305,21703188,21973079,and 21933012)the National Key R&D Program of China(no.2017YFA0204902)+2 种基金supported by the FET Open project 767187-QuIETthe EU project BAC-TO-FUELthe UK EPSRC grants EP/N017188/1 and EP/M014452/1 in Lancaster.
文摘The emergence of molecular spintronics offers a unique chance for the design of molecular devices with different spin-states,and the control of spin-state becomes essential for molecular spin switches.However,the intrinsic spin switching from low-to high-spin state is a temperature-dependent process with a small energy barrier where low temperature is required to maintain the low-spin state.Thus,the room-temperature operation of single-molecule devices has not yet been achieved.Herein,we present a reversible single-molecule conductance switch by manipulating the spin states of the molecule at room temperature using the scanning tunneling microscope break-junction(STM-BJ)technique.The manipulation of the spin states between S=0 and S=1 is achieved by complexing or decomplexing the pyridine derivative molecule with a square planar nickel(Ⅱ)porphyrin.The bias-dependent conductance evolution proves that the strong electric field between the nanoelectrodes plays a crucial role in the coordination reaction.The density functional theory(DFT)calculations further reveal that the conductance changes come from the geometric changes of the porphyrin ring and spin-state switching of the Ni(Ⅱ)ion.Our work provides a new avenue to investigate room-temperature spin-related sensors and molecular spintronics.
