More aromatic molecular junction has lower conductance

Xie, Zhen; Ji, Xiaoli; Song, Yang; Wei, Mingzhi; Wang, Chuan‐Kui

doi:10.1016/j.cplett.2015.09.017

Cited by 12 publications

(10 citation statements)

References 43 publications

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“…More aromatic rings with higher resonance energies were seen to correlate with HOMO (highest occupied molecular orbital) positions further from the Fermi level and lower conductance (which in these molecules is HOMO dominated)17. Subsequent transport calculations verified this trend and reported smaller molecular gaps and HOMO positions closer to the Fermi level with decreasing aromaticity18. However, the chemical instability of the antiaromatic molecules and unfavourable intermolecular interaction in the bulk has restricted transport studies to aromatic systems or species with no aromaticity.…”

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confidence: 78%

Highly-conducting molecular circuits based on antiaromaticity

et al. 2017

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Aromaticity is a fundamental concept in chemistry. It is described by Hückel’s rule that states that a cyclic planar π-system is aromatic when it shares 4n+2 π-electrons and antiaromatic when it possesses 4n π-electrons. Antiaromatic compounds are predicted to exhibit remarkable charge transport properties and high redox activities. However, it has so far only been possible to measure compounds with reduced aromaticity but not antiaromatic species due to their energetic instability. Here, we address these issues by investigating the single-molecule charge transport properties of a genuinely antiaromatic compound, showing that antiaromaticity results in an order of magnitude increase in conductance compared with the aromatic counterpart. Single-molecule current–voltage measurements and ab initio transport calculations reveal that this results from a reduced energy gap and a frontier molecular resonance closer to the Fermi level in the antiaromatic species. The conductance of the antiaromatic complex is further modulated electrochemically, demonstrating its potential as a high-conductance transistor.

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confidence: 78%

Highly-conducting molecular circuits based on antiaromaticity

et al. 2017

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“…This back and forth journey between chemistry and physics is fortunately well known. This is the case of concepts such as aromaticity or electron delocalization, which have been recently related to, respectively, quantum interference effects in molecular junctions [12][13][14][15][16][17][18][19][20][21][22][23] and formation of soliton states 24 in onedimensional topological insulators, TIs. Namely, it has been predicted theoretically and later conrmed experimentally that aromaticity may exert a positive/negative effect on the conducting ability of organic conjugated chains.…”

Section: Introductionmentioning

confidence: 99%

Anti-ohmic single molecule electron transport: is it feasible?

et al. 2019

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“…We study several pairs of aromatic‐antiaromatic and antiaromatic‐quinoidal molecules (Figure 1) which represent prototypical backbones for electron transport studies [1,2,9–18,22–29] . Calculation of their Nucleus‐Independent Chemical Shifts (NICS), establishing their (anti)aromatic character, are given in SI section 1.…”

Section: Resultsmentioning

confidence: 99%

“…We study several pairs of aromatic-antiaromatic and antiaromatic-quinoidal molecules (Figure 1) which represent prototypical backbones for electron transport studies. [1,2,[9][10][11][12][13][14][15][16][17][18][22][23][24][25][26][27][28][29] Calculation of their Nucleus-Independent Chemical Shifts (NICS), establishing their (anti)aromatic character, are given in SI section 1. We derive antiaromatic oligoacenes by removing two C atoms from a benzene ring, effectively replacing a benzene ring in the aromatic molecule with a cyclobutadiene ring.…”

Section: Resultsmentioning

confidence: 99%

“…[1,2] On the basis of electrochemical measurements of oxidation/reduction potentials, antiaromatic compounds were long predicted to lead to higher conductance than aromatic backbones, but their instability hindered their study. [8][9][10] Aromaticity was shown to negatively correlate with conductance [11] as the least aromatic compounds had molecular resonances closer to the Fermi level, [12] leading to increased conductance. In the few exper-imental studies of genuinely antiaromatic molecules available so far, some showed increased conductance compared with aromatic analogues, [13,14] but in other cases this expected effect was not observed.…”

Section: Introductionmentioning

confidence: 99%

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Origin of the Electron Transport Properties of Aromatic and Antiaromatic Single Molecule Circuits

Arasu

Vázquez

2021

ChemPhysChem

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Antiaromatic molecules have been predicted to exhibit increased electron transport properties when placed between two nanoelectrodes compared to their aromatic analogues. While some studies have demonstrated this relationship, others have found no substantial increase. We use atomistic simulations to establish a general relationship between the electronic spectra of aromatic, antiaromatic, and quinoidal molecules and illustrate its implications for electron transport. We compare the electronic properties of a series of aromatic‐antiaromatic counterparts and show that antiaromaticity effectively p‐dopes the aromatic electronic spectra. As a consequence, the conducting properties of aromatic‐antiaromatic analogues are closely related. For similar attachment points to the electrodes, an interference feature is expected in the HOMO‐LUMO gap of one whenever it is absent in the other one. We demonstrate how the relative conductance of aromatic‐antiaromatic pairs can be tuned and even reversed through the choice of chemical linker groups. Our work provides a general picture relating connectivity, (anti)aromaticity, and quantum interference and establishes new design rules for single molecule circuits.

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More aromatic molecular junction has lower conductance

Cited by 12 publications

References 43 publications

Highly-conducting molecular circuits based on antiaromaticity

Highly-conducting molecular circuits based on antiaromaticity

Anti-ohmic single molecule electron transport: is it feasible?

Origin of the Electron Transport Properties of Aromatic and Antiaromatic Single Molecule Circuits

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