Aromaticity Decreases Single-Molecule Junction Conductance.

Chen, Wenbo; Li, Haixing; Widawsky, Jonathan R.; Appayee, Chandrakumar; Venkataraman, Latha; Breslow, Ronald

doi:10.1021/ja411143s

Cited by 152 publications

(195 citation statements)

References 13 publications

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“…It shows that when the molecules are adsorbed on pyramidal protruding or single atom protruding electrode surfaces, the conductance of these junctions show a negative relationship with their aromaticity, which is consistent with the experimental finding [34]. The analysis of the transmission coefficients and the molecular projected self-consistent Hamiltonian attributes this to the aromaticity dependent alignment of frontier molecular orbitals with the Fermi energy of electrodes.…”

supporting

confidence: 86%

More aromatic molecular junction has lower conductance

Xie

Song

et al. 2015

Chemical Physics Letters

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supporting

confidence: 86%

More aromatic molecular junction has lower conductance

Xie

Song

et al. 2015

Chemical Physics Letters

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“…[47] As we expected, 29 was the best conductor and the commonly used thiophene 27 was the worst, with 28 in between. Thus here aromatic stabilization clearly diminishes conductivity, an effect that has been previously ignored.…”

Section: Our Recent Interest In Aromaticity and Antiaromaticitymentioning

confidence: 51%

Novel Aromatic and Antiaromatic Systems

Breslow

2014

The Chemical Record

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Note from the Editor: August Kekulé's dream and his theory of the structure of benzene (1865). Julius Thomsen's logic that benzene contains equivalent electrons between its carbon atoms (ca. 1900). Richard Willstätter's synthesis and observation that 1,3,5,7‐cyclooctatetraene is not aromatic (early 1900s). Sir Robert Robinson's proposal of the ‘aromatic sextet’ (1925). Erich Hückel's molecular orbital treatment of benzene and other unsaturated compounds that separated sigma and pi electrons (early 1930s). Tetsuo Nozoe and Michael Dewar's independent proposal of a new aromatic structure for a cycloheptatrieneone (mid‐1940s). Ronald Breslow's demonstration that cyclopropenyl cation is aromatic (1958). Breslow's proposal of ‘antiaromaticity’ (1965). I offer several comments. First, in the field of aromaticity, Breslow is in mighty exceptional company. Second, his research has extended well beyond aromaticity. Yes, Breslow is applying the concepts of antiaromaticity toward the development of highly conductive organic materials. But his research has encompassed enzyme mimics, remote functionalization reactions, unnatural DNA analogues and cancer chemotherapy. Indeed, Breslow is the co‐discoverer of a highly successful drug, Vorinostat, which is FDA‐approved for the treatment of cutaneous T‐cell lymphoma. We thank Professor Breslow for joining our project honoring his and our friend, Tetsuo Nozoe. Tetsuo Nozoe would have would have been deeply touched. —Jeffrey I. Seeman Guest Editor University of Richmond Richmond, Virginia 23173, USA E‐mail: jseeman@richmond.edu Ronald Breslow with Koji Nakanishi (left) and Tetsuo Nozoe (center), Sendai, 1970. Abstract We contributed to the field of non‐benzenoid aromatic compounds by creating the cyclopropenyl cation and various of its derivatives, including cyclopropenone; it was the first aromatic system with other than six pi electrons in a single ring, and the simplest aromatic system. The pioneering work of Tetsuo Nozoe in tropolone chemistry was celebrated with the founding of ISNA, the International Symposium on Non‐Benzenoid Aromatic Compounds, where I described our work in the field. It fit the prediction that aromaticity would be found in systems with 4n + 2 pi electrons, where n is an integer. I was also concerned with the properties of monocyclic systems with 4n cyclically conjugated pi electrons. They were expected not to be aromatic, but the interesting question was whether they were actually antiaromatic, especially destabilized by the cyclic conjugation in such 4n species as the cyclopropenyl anion, cyclobutadiene, and cyclopentadienyl cation. The evidence supports antiaromaticity in these cases. We also examined compounds where 4n cyclic pi systems were fused with aromatic systems, and most interestingly systems in which two 4n pi systems were fused. In these cases the periphery of the molecules had 4n + 2 pi electrons, for aromaticity, but the components were antiaromatic. Recently we have studied electrical conductivities in aromatic molecules such as thiophe...

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“…Closely related to this point, interference effects raising from ring electron currents which opposes to electron transmission in aromatic molecules have been theoretically investigated [37,38]. Also, experimental evidences of a negative relation between aromaticity and conductance have been reported recently [39,40]. Results of Ref.…”

Section: Electric Conductance and Aromatic Stabilizationmentioning

confidence: 87%