Switching of functionalized azobenzene suspended between gold tips by mechanochemical, photochemical, and opto-mechanical means

Turanský, Robert; Konôpka, Martin; Doltsinis, Nikos L.; Štich, Ivan; Marx, Dominik

doi:10.1039/c0cp00588f

Cited by 65 publications

(93 citation statements)

References 66 publications

(91 reference statements)

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“…This strategy has been in fact used for azobenzene by Bockmann et al [15] who used density functional theory (DFT)-based ab initio molecular dynamics simulations to set up a GROMOS-like MM description of azobenzene (diphenyldiazene, 1-DA in the following). This description was later exploited to study azobenzene's containing systems in a variety of applications [16][17][18]. Moreover, a classical force field for a peptide derivative of azobenzene has been set up to simulate AFM experiments [19].…”

Section: Introductionmentioning

confidence: 99%

First-principle-based MD description of azobenzene molecular rods

et al. 2012

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Extensive density functional theory (DFT) calculations have been performed to develop a force field for the classical molecular dynamics (MD) simulations of various azobenzene derivatives. Besides azobenzene, we focused on a thiolated azobenzene's molecular rodthat has been previously demonstrated to photoisomerize from trans to cis with high yields on surfaces. The developed force field is an extension of OPLS All Atoms, and key bonding parameters are parameterized to reproduce the potential energy profiles calculated by DFT. For each of the parameterized molecule, we propose three sets of parameters: one best suited for the trans configuration, one for the cis configuration, and finally, a set able to describe both at a satisfactory degree. The quality of the derived parameters is evaluated by comparing with structural and vibrational experimental data. The developed force field opens the way to the classical MD simulations of selfassembled monolayers (SAMs) of azobenzene's molecular rods, as well as to the quantum mechanics/molecular mechanics study of photoisomerization in SAMs.

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Section: Introductionmentioning

confidence: 99%

First-principle-based MD description of azobenzene molecular rods

et al. 2012

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“…Additional question-marks mar the photo-switchability of anchored AB photo-switches. While anchored polymeric chains of AB molecules are easily switchable optically [28], switching of their tip/surface-anchored single AB counterpart was found to be mechanically hindered [9,10]. In order to eliminate the mechanical hindrance a variant of an anchored single-molecule AB switch using a conducting carbon nano-tube support for one electrode was proposed [7].…”

Section: Introductionmentioning

confidence: 99%

“…However, use of these optoelectronic devices requires that their operation be reversible. While there are numerous molecules capable of photo-switching in gas-phase, their embedding in junction by anchoring to tips or surfaces may compromise their switching capability either due to mechanical hindrance [9,10] or quenching of excited state in the photo-switchable process [21].…”

Section: Introductionmentioning

confidence: 99%

“…This is typically achieved by modifying the molecular conformation. Change of the conformation may be driven by electric currents [11][12][13], tip of an AFM/STM apparatus [4,5,9,10,[14][15][16][17], or by electromagnetic radiation [6][7][8][9][10][18][19][20]. The primary advantage of light-driven optoelectronic devices is their fast switching speed [6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

“…Molecular electronics is undoubtedly a promising complementary technology to semiconductor-based electronics [1][2][3][4][5][6][7][8][9][10]. The molecule used to fabricate a nano-scale device must be capable of rectification, amplification, or switching.…”

Section: Introductionmentioning

confidence: 99%

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Rigidity of the conductance of an anchored dithioazobenzene optomechanical switch

2013

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Reversible opto-mechanical molecular switch based on a single azobenzene molecule suspended via thiolate links between realistic models of gold tips is investigated. Using a combination of the transfer matrix technique and density functional theory we focus on conductance of the nano-device in the two (meta)stable cis and trans junction conformations. We find the conductance of both conformations to be broadly similar. In qualitative agreement with related experiments, we find that the same nano-device with one/two methylene linker group(s) inserted on one/both ends of the azobenzene molecule is driven into tunneling regime and reduces the conductances by up to two orders of magnitude, again almost uniformly for both conformations. These results clarify the huge differences in switching ratios found previously and indicate that this nano-device is not particularly suited for use as a molecular switch based on conductance change.

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Barrierless Single‐Electron‐Induced cis–trans Isomerization

Klaiman

Cederbaum

2015

Angewandte Chemie

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Lowering the activation energy of ac hemical reaction is an essential part in controlling chemical reactions. By attachingasingle electron, ab arrierless path for the cistrans isomerization of maleonitrile on the anionic surface is formed. The anionic activation can be applied in both reaction directions,y ielding the desired isomer.W ei dentify the microscopic mechanism that leads to the formation of the barrierless route for the electron-induced isomerization. The generalization to other chemical reactions is discussed. Theabilitytosurpasstheenergeticbarrierbetweenreactantsand products is at the very heart of controlling chemical reactions.V arious control strategies have been developed over the years that rely,f or example,o nt he use of light, mechanical force,o re lectric current. Regardless of the chosen external stimulation, the common strategy is either to move the reaction to ad ifferent potential energy surface, for example,p hotochemistry, [1] or to modify the potential energy surface of the reactants,f or example,m echanochemistry.[2] Ideally,t he target potential energy surface does not only energetically enable the reaction but provides ac lear directionality as well.Thei dea of activating ac hemical reaction by attaching as ingle electron has been around since the early days of electrochemistry.S till, the prominent role of the electron in many reactions has been restricted to inducing adissociative electron attachment (DEA) mechanism. Them ain use of DEA in promoting chemical reactions is through the creation of radicals that continue to react further.[3] Only in the past decade,e xperiments demonstrating more complicated reactions following electron capture have emerged, for example, multiple bond-breaking, [4] tautomerization, [5] and complex fragmentations.[6] Theu nderlying microscopic mechanism that leads to the electron-driven chemistry in the above examples is still unknown. There have also been af ew theoretical works predicting multiple bond-breaking rearrangements following electron attachment. [7] Herein we demonstrate how the attachment of as ingle electron can lead to ab arrierless cis-trans isomerization of maleonitrile (cis-1,2-dicyanoethylene,MN) and fumaronitrile (trans-1,2-dicyanoethylene,FN). Theexcess electron transfers the reactants to the anionic potential energy surface (PES) on which there is no longer an energetic barrier towards isomerization. By analyzing the microscopic mechanism responsible for this appealing topology,wegain new insights into the yet unexplored possibilities of electron-driven chemistry.The cis-trans isomerization reaction is one of the most studied reactions with regard to chemical control and chemical switching,f or example by light [8] or mechanical force.[9] Very recently it has been shown that the cis-trans isomerization rate can be tuned by the presence of an earby anion. [10] Thei somerization of FN to MN was previously studied using photoinduced electron transfer. [11] In these experiments the FN À anion is formed in its ground state ...

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Switching of functionalized azobenzene suspended between gold tips by mechanochemical, photochemical, and opto-mechanical means

Cited by 65 publications

References 66 publications

First-principle-based MD description of azobenzene molecular rods

First-principle-based MD description of azobenzene molecular rods

Rigidity of the conductance of an anchored dithioazobenzene optomechanical switch

Barrierless Single‐Electron‐Induced cis–trans Isomerization

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