TY - JOUR
T1 - Light-Induced Conversion of Chemical Permeability to Enhance Electron and Molecular Transfer in Nanoscale Assemblies
AU - Balgley, Renata
AU - de Ruiter, Graham
AU - Evmenenko, Guennadi
AU - Bendikov, Tatyana
AU - Lahav, Michal
AU - van der Boom, Milko E
N1 - Funding Information: This research was supported by the Ministry of Science, Technology and Space, Israel, the Helen and Martin Kimmel Center for Molecular Design, Mary and Tom Beck-Canadian Center for Alternative Energy Research, David Rosenberg (Chicago, IL), the Yeda-Sela Center for Basic Research, a research grant from the Leona M. and Harry B. Helmsley Charitable Trust, the Israel Science Foundation (ISF) Grant No. 1023/13. G.E. gratefully acknowledges support from the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Publisher Copyright: © 2016 American Chemical Society.
PY - 2016/12/21
Y1 - 2016/12/21
N2 - In this paper, we demonstrate how photo chemically enhancing the permeability of metal-organic assemblies results in a significant enhancement of the electrochemical activity of metal complexes located within the assembly. The molecular assemblies consist of different layers of redox-active metal complexes ([M(mbpy-py)(3)][PF6](2); M = Ru or Os) that are separated by redox-inactive spacers consisting of 1,4-bis[2-(4-pyridyl)ethenyl]benzene (BPEB) and PdCl2 of variable thicknesses (0-13.4 nm). UV-irradiation (lambda = 254 nm) of our assemblies induces a photochemical reaction in the redox-inactive spacer increasing the permeability of the assembly. The observed increase was evident by trapping organic ((Bu4NBF4)-Bu-n) and inorganic (NiCl2) salts inside the assemblies, and by evaluating the electrochemical response of quinones absorbed inside the molecular assemblies before and after UV irradiation. The increase in permeability is reflected by higher currents and a change in the directionality of electron transfer, i.e., from mono- to bidirectional, between the redox-active metal complexes and the electrode surface. The supramolecular structure of the assemblies dominates the overall electron transfer properties and overrules possible electron transfer mediated by the extensive pi-conjugation of its individual organic components.
AB - In this paper, we demonstrate how photo chemically enhancing the permeability of metal-organic assemblies results in a significant enhancement of the electrochemical activity of metal complexes located within the assembly. The molecular assemblies consist of different layers of redox-active metal complexes ([M(mbpy-py)(3)][PF6](2); M = Ru or Os) that are separated by redox-inactive spacers consisting of 1,4-bis[2-(4-pyridyl)ethenyl]benzene (BPEB) and PdCl2 of variable thicknesses (0-13.4 nm). UV-irradiation (lambda = 254 nm) of our assemblies induces a photochemical reaction in the redox-inactive spacer increasing the permeability of the assembly. The observed increase was evident by trapping organic ((Bu4NBF4)-Bu-n) and inorganic (NiCl2) salts inside the assemblies, and by evaluating the electrochemical response of quinones absorbed inside the molecular assemblies before and after UV irradiation. The increase in permeability is reflected by higher currents and a change in the directionality of electron transfer, i.e., from mono- to bidirectional, between the redox-active metal complexes and the electrode surface. The supramolecular structure of the assemblies dominates the overall electron transfer properties and overrules possible electron transfer mediated by the extensive pi-conjugation of its individual organic components.
UR - https://www.scopus.com/pages/publications/85006858175
U2 - 10.1021/jacs.6b09781
DO - 10.1021/jacs.6b09781
M3 - Article
C2 - 27936654
SN - 0002-7863
VL - 138
SP - 16398
EP - 16406
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 50
ER -