break-junction technique; fluoride ions; quantum interference; scanning tunneling microscopy; single-molecule charge transport; Break junctions; Charge transport through molecules; Fluoride ion; Quantum interference effects; Sensing applications; Single molecule; Single molecule conductance; Catalysis; Organic Chemistry; General Chemistry
Abstract :
[en] Providing a chemical control over charge transport through molecular junctions is vital to developing sensing applications at the single-molecule scale. Quantum-interference effects that affect the charge transport through molecules offer a unique chance to enhance the chemical control. Here, we investigate how interference effects can be harnessed to optimize the response of single molecule dithienoborepin (DTB) junctions to the specific coordination of a fluoride ion in solution. The single-molecule conductance of two DTB isomers is measured using scanning tunneling microscopy break-junction (STM-BJ) before and after fluoride ion exposure. We find a significant change of conductance before and after the capture of a fluoride ion, the magnitude of which depends on the position of the boron atom in the molecular structure. This single-molecule sensor exhibits switching ratios of up to four orders of magnitudes, suggesting that the boron-fluoride coordination can lead to quantum-interference effects. This is confirmed by a quantum chemical characterization, pointing toward a cross-conjugated path through the molecular structure as the origin of the effect.
Disciplines :
Physics
Author, co-author :
Baghernejad, Masoud ; Transport at Nanoscale Interface Laboratory, Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600, Dübendorf, Switzerland ; Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012, Bern, Switzerland ; Department of Physics, University of Basel, Klingelbergstrasse 56, 4056, Basel, Switzerland
Van Dyck, Colin ; Université de Mons - UMONS > Faculté des Sciences > Service Chimie Physique Théorique
Bergfield, Justin; Department of Physics and Department of Chemistry, Illinois State University, Moulton Hall, USA
Levine, David R; Department of Chemistry and Department of Materials Science and Engineering, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD, 21218, USA
Gubicza, Agnes; Transport at Nanoscale Interface Laboratory, Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600, Dübendorf, Switzerland
Tovar, John D; Department of Chemistry and Department of Materials Science and Engineering, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD, 21218, USA
Calame, Michel; Transport at Nanoscale Interface Laboratory, Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600, Dübendorf, Switzerland ; Department of Physics, University of Basel, Klingelbergstrasse 56, 4056, Basel, Switzerland
Broekmann, Peter; Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012, Bern, Switzerland
Hong, Wenjing; Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012, Bern, Switzerland ; State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, NEL, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Language :
English
Title :
Quantum Interference Enhanced Chemical Responsivity in Single-Molecule Dithienoborepin Junctions.
Northwestern University National Science Foundation
Funding text :
Partial financial support by EC H2020 FET Open RECORD-IT (no. 606728), Swiss National Science Foundation as part of the NCCR Molecular Systems Engineering is acknowledged. The work of C.V.D. has been supported by the Belgian American Education Foundation (BAEF) and was mainly done as a postdoctoral fellow of Northwestern University. C.V.D. also acknowledges the support of the National Research Council of Canada and the University of Mons. We gratefully acknowledge the Laboratory for Chemistry of Novel Materials at the University of Mons for access to their computational resources. Work at Johns Hopkins was supported by the US National Science Foundation (CHE-1464798).
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