Rectifying enhancement induced by conjugation breaking in thiolated arylethynylene single-molecular diodes

Rectifying properties of three cyano side group substituted arylethynylene thiolate molecules are theoretically investigated based on abinitio calculations. The current-voltage curves show that rectifying performance of the junctions correlates negatively with conjugation of the molecules, which reveals a much more pronounced rectification behavior for that with broken-conjugated dihydroanthracene core (sAH) than the counterpart with linearly-conjugated anthracene core (sAC) or cross-conjugated anthraquinone core (sAQ). It is demonstrated that the conjugation breaking induced localization of molecular orbital and asymmetric evolution of its spatial distribution under positive and negative biases play the key role for the rectification enhancement in sAH. (C) 2016 Elsevier B.V. All rights reserved.