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Issue 7, 2015
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Charge transfer versus molecular conductance: molecular orbital symmetry turns quantum interference rules upside down

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Abstract

Destructive quantum interference has been shown to strongly reduce charge tunneling rates across molecular bridges. The current consensus is that destructive quantum interference occurs in cross-conjugated molecules, while linearly conjugated molecules exhibit constructive interference. Our experimental results on photoinduced charge transfer in donor-bridge-acceptor systems, however, show that hole transfer is ten times faster through a cross-conjugated biphenyl bridge than through a linearly conjugated biphenyl bridge. Electronic structure calculations reveal that the surprisingly low hole transfer rate across the linearly conjugated biphenyl bridge is caused by the presence of destructive instead of constructive interference. We find that the specific molecular orbital symmetry of the involved donor and acceptor states leads to interference conditions that are different from those valid in single molecule conduction experiments. Furthermore, the results indicate that by utilizing molecular orbital symmetry in a smart way new opportunities of engineering charge transfer emerge.

Graphical abstract: Charge transfer versus molecular conductance: molecular orbital symmetry turns quantum interference rules upside down

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Publication details

The article was received on 27 Mar 2015, accepted on 08 May 2015 and first published on 11 May 2015


Article type: Edge Article
DOI: 10.1039/C5SC01104C
Citation: Chem. Sci., 2015,6, 4196-4206
  • Open access: Creative Commons BY-NC license
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    Charge transfer versus molecular conductance: molecular orbital symmetry turns quantum interference rules upside down

    N. Gorczak, N. Renaud, S. Tarkuç, A. J. Houtepen, R. Eelkema, L. D. A. Siebbeles and F. C. Grozema, Chem. Sci., 2015, 6, 4196
    DOI: 10.1039/C5SC01104C

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