Toward a Light-Driven Motorized Nanocar: Synthesis and Initial Imaging of Single Molecules

Chiang, Pinn-Tsong; Mielke, Johannes; Godoy, Jazmin; Guerrero, Juan M.; Alemany, Lawrence B.; Villagómez, Carlos J.; Saywell, Alex; Grill, Leonhard; Tour, James M.

doi:10.1021/nn203969b

Cited by 119 publications

(117 citation statements)

References 29 publications

Supporting

Mentioning

116

Contrasting

Unclassified

Order By: Relevance

“…A key aspect of fulfilling the potential of synthetic rotary molecular motors for future applications in, e.g., molecular transport 42 and as tools for rotating objects much larger than themselves, 43 is reaching high rotational frequencies under ambient conditions. 24,44 A major experimental effort has therefore been invested in accelerating the rate-limiting thermal steps of overcrowded alkene-based rotary molecular motors, 18,19,21,[23][24][25]27,28,33 exploring the influence of conformational, steric and electronic factors.…”

Section: Methodsmentioning

confidence: 99%

Computational design of faster rotating second-generation light-driven molecular motors by control of steric effects

Oruganti

Fang

Durbeej

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We report a systematic computational investigation of the possibility to accelerate the rate-limiting thermal isomerizations of the rotary cycles of synthetic light-driven overcrowded alkene-based molecular motors through modulation of steric interactions.Choosing as reference system a second-generation motor known to accomplish rotary motion in the MHz regime and using density functional theory methods, we propose a three-step mechanism for the thermal isomerizations of this motor and show that variation of the steric bulkiness of the substituent at the stereocenter can reduce the (already small) free-energy barrier of the rate-determining step by a further 15−17 kJ mol -1 . This finding holds promise for future motors of this kind to reach beyond the MHz regime. Furthermore, we demonstrate and explain why one particular step is kinetically favored by decreasing and another step is kinetically favored by increasing the steric bulkiness of this substituent, and identify a possible back reaction capable of impeding the rotary rate.3

show abstract

Section: Methodsmentioning

confidence: 99%

Computational design of faster rotating second-generation light-driven molecular motors by control of steric effects

Oruganti

Fang

Durbeej

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…[23] Furthermore, while molecular motors are generally synthesized and tested in solution, a number of studies have demonstrated that many overcrowded alkenes maintain their rotary function also when attached to inorganic surfaces, [25,[36][37][38] which is widely regarded a key step in exerting control of the motors in future nanodevices. In other developments, overcrowded alkenes have been used as motors for propelling so-called nanocars along surfaces, [24,[39][40][41] thus effectively transforming their rotary motion into translation. In one such design shown in Figure 2, a rotary motor propels a nanocar with four C 60 wheels.…”

Section: R Ota R Y M Ol Ecu L a R Mot Orsmentioning

confidence: 99%

Quantum chemical design of rotary molecular motors

Oruganti

Wang

Durbeej

2017

Int J of Quantum Chemistry

View full text Add to dashboard Cite

This tutorial review describes how recent quantum chemical calculations and non-adiabatic molecular dynamics simulations have provided valuable guidelines and insights for the design of more powerful synthetic rotary molecular motors. Following a brief overview of the various types of rotary motors synthesized to date, we present computationally identified steric and electronic approaches to significantly reduce the free-energy barriers of the critical thermal isomerization steps of chiral overcrowded alkenes, a main class of motors whose potential for many different kinds of applications is well documented. Furthermore, we describe how computational research in this field has provided new motor designs that differ from overcrowded alkenes by either (1) completing a full 3608 rotation through fewer steps, (2) exhibiting more efficient photochemical steps, or (3) requiring fewer chiral features for their function, including a design that even in the absence of a stereocenter achieves unidirectional rotary motion from two Z/E photoisomerizations alone.chirality, molecular motors, non-adiabatic molecular dynamics, photoisomerization, steric interactions | I N TR ODU C TI ONIn this tutorial review, we give an account of how quantum chemical research has contributed to advance the field of artificial molecular machines.This field [1][2][3][4][5][6][7][8][9][10][11] is devoted to the fabrication of molecular systems capable of performing the same type of machine-like functions that Nature-made protein complexes carry out in order to, among other things, propel cells, store energy in cells, equip cells with transport systems, and generate biomechanical forces. [12][13][14] Although artificial molecular machines are yet to make an impact on our everyday lives, the field is currently undergoing a rapid expansion both in terms of what man-made molecules can accomplish and the areas of expertise of the scientists drawn to the field. In many ways, this development, envisioned already in 1959 by Richard Feynman in his prophetic "There's Plenty of Room at the Bottom" lecture, [15] is testament to the groundbreaking work on the design and synthesis of molecular machines [16][17][18][19][20][21][22][23][24][25] for which Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard (Ben) L. Feringa were awarded the Nobel Prize in Chemistry 2016.While a molecular machine can be defined as "an assembly of a discrete number of molecular components designed to perform mechanical-like movements (output) as a consequence of appropriate external stimuli (input)," [2] this tutorial review focuses on the subset of such systems known as molecular motors. Loosely speaking, molecular motors are molecules that can produce net work by absorbing external energy and converting the energy into directed (non-random) mechanical motion in a controllable fashion. The ability to produce net work is the distinguishing feature of molecular motors vis-a-vis molecular switches, the latter of which sustain back-and-forth motion but not the continuous m...

show abstract

“…1c), one of a family of nanovehicles, termed nanocars. [24][25][26] The use of only one motor per vehicle eliminates the need for chiral resolutions in the synthesis since each motor has only one sense of possible rotary motion. Thus, opposing directional forces that can hinder translation in the case of two or more motors, as observed previously, 18 are avoided.…”

Section: Resultsmentioning

confidence: 99%

Light-Induced Translation of Motorized Molecules on a Surface

et al. 2016

Self Cite

View full text Add to dashboard Cite

Molecular machines are a key component in the vision of molecular nanotechnology, and have the potential to transport molecular species and cargo on surfaces. The motion of such machines should be triggered remotely, ultimately allowing a large number of molecules to be propelled by a single source, with light being an attractive stimulus. Here, we report upon the photo-induced translation of molecular machines across a surface by characterizing single molecules before and after illumination. Illumination of molecules containing a motor unit results in an enhancement in the diffusion of the molecules. The effect vanishes if an incompatible photon energy is used or if the motor unit is removed from the molecule, revealing that the enhanced motion is due to the presence of the wavelength-sensitive motor in each molecule.Molecular machines with internal motors are fascinating objects that transform energy into useful motion at the nanoscale. [1][2][3][4][5][6] In nature many processes depend on molecular motors that perform specific mechanical tasks in living cells, 7 a prototypical process is the directional motion of myosin. 8 Several synthetic molecular motors have been synthesized, 2,9,10 including a molecular motor developed by Feringa and co-workers that rotates at a frequency in the MHz regime. [11][12][13][14] For ultimate control of molecular machines it is essential that the motor exhibits only one sense of rotation, resulting in unidirectional translation of the molecular machine on a surface, thus only forward and no backward motion, in contrast to random motion in all directions. 2 For synthetic molecular machines to contribute to the vision of nanotechnology by transporting molecular species and cargo on surfaces, the motion of

show abstract

Toward a Light-Driven Motorized Nanocar: Synthesis and Initial Imaging of Single Molecules

Cited by 119 publications

References 29 publications

Computational design of faster rotating second-generation light-driven molecular motors by control of steric effects

Computational design of faster rotating second-generation light-driven molecular motors by control of steric effects

Quantum chemical design of rotary molecular motors

Light-Induced Translation of Motorized Molecules on a Surface

Contact Info

Product

Resources

About