A single-molecule blueprint for synthesis

Stone, Ilana B.; Starr, Rachel L.; Zang, Yaping; Nuckolls, Colin; Steigerwald, Michael L.; Lambert, Tristan H.; Roy, Xavier; Venkataraman, Latha

doi:10.1038/s41570-021-00316-y

Cited by 34 publications

(31 citation statements)

References 162 publications

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“…41,[62][63][64][65][66] Thus, by triggering the excitaOon strength, a local-probe Op is able to prompt conformaOonal changes 67,68 and even breaking/formaOon of chemical bonds. 49,[69][70][71][72][73][74][75][76][77] Applying localized voltage pulses with an STM Op on the keto group of molecules on Cu(111) at 5 K, we reproducibly observed the irreversible transformaOon of the molecules. We considered two possible mechanisms to explain these facts: (i) a stable keto-enol transfer stabilized by the surface and (ii) the formaOon of a vacancy on the copper surface with consequent formaOon of a complex between the oxygen atoms of the molecule and the metallic adatoms extracted from the surface.…”

Section: Figure 1 Leand Representa-on Of the Diketo Indigo Molecule (...mentioning

confidence: 85%

“…It is now well established that STM manipulations can be performed according to three different strategies. First, by using mechanical lateral forces between the tip and the adsorbate, one can pull, slide, or push a molecule or an atom between definite positions on the surface. − Second, the localized electric field, enhanced by the tip effect, can induce a controlled motion of the adsorbate, ,− as exemplified by the recent nanocar race. − Finally, the current of energetic tunnel electrons can chemically modify the conformation of a molecular adsorbate. ,− Thus, by triggering the excitation strength, a local-probe tip is able to prompt conformational changes , and even breaking/formation of chemical bonds. ,− …”

Section: Introductionmentioning

confidence: 99%

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Surface Vacancy Generation by STM Tunneling Electrons in the Presence of Indigo Molecules on Cu(111)

et al. 2022

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Herein, we invesOgate the consequence of local voltage pulses on the adsorpOon state of single indigo molecules on the Cu(111) surface as well as on the atomic structure underneath the molecule. With a scanning tunneling microscope, at 5 K, intact molecules are imaged as two lobes corresponding to the electron density of each indoxyl moiety of the molecule which are connected by a carbon double bond. Then, two short successive voltage pulses with the Op placed above the molecule generate irreversible modificaOons, as revealed by consecuOve scanning tunneling microscopy (STM) imaging. Density-funcOonal theory calculaOons coupled to STM image calculaOons indicate the creaOon of a double surface vacancy of copper surface atoms below the oxygen atom of the indigo molecule as the most plausible scenario. These extracted copper atoms are stabilized as adatoms by the indigo oxygens, oxidizing each copper adatom to 0.32 electron. Introduc0onThe indigo molecule is an ancient organic dye molecule that has been used for centuries to dye colorful blue color texOles, and they even appear in recipes of Babylonian transcripts. 1 Nowadays, it is widely used as a pigment to dye billions of blue jeans per year. 2 On the other hand, due to the electronic, opOcal, and chemical properOes of the indigo molecule and its derivaOves, several applicaOons are explored such as field-effect transistors, 3,4 solar cells, 5,6 diodes, 7-9 memory storage devices, 10 diesel markers, 11 DNA biosensors, 12 or chemical detectors of NO 2 . 13 Also, the chemical structure of indigo moOvates exploring new chromophores with greater optoelectronic features. 14,15 There exist wide literature reports on indigo and its derivaOves with regard to the high photostability of the compounds. Three phenomena are invoked to account for an intramolecular change causing photostability: (1) photoexcitaOon of an excited state of the molecule for trans-cis isomerizaOon through the C═C bond; (2) isomeric change from the keto to monoenol configuraOon (Figure 1) by excited-state intramolecular proton (ESIP) transfer, where the hydrogen atom of the nitrogen atom is transferred to the oxygen; finally, (3) the isomeric dienol configuraOon resulOng from excited-state dual proton (ESDP) transfer, where both hydrogen atoms of the amine central groups are transferred to both oxygen atoms of the carbonyl groups. The first mechanism appears less favorable due to steric crowding between hydrogen atoms in the final form and the important interacOon of the hydrogen bonding between the carbonyl and N-H groups. [16][17][18][19][20] However, some thioindigo derivaOves show trans-cis isomerizaOon and the involvement of a triple state in the photoisomerizaOon 21,22 and parOcularly N,N′-di(tbutoxycarbonyl)indigo 23 shows the absence of intramolecular N-H•••O bonding. The photostability of indigo is thus been aiributed to the ESIP transfer from the keto to enol intramolecular isomerizaOon ajer irradiaOon (Figure 1), where the proton transfer occurs from the nitrogen to the oxygen atoms at th...

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Section: Figure 1 Leand Representa-on Of the Diketo Indigo Molecule (...mentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Surface Vacancy Generation by STM Tunneling Electrons in the Presence of Indigo Molecules on Cu(111)

et al. 2022

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Section: Single‐molecule Electrical Platformsmentioning

confidence: 99%

“…Break junction techniques, including scanning tunneling microscope break junction and mechanically controllable break junction, usually aim to characterize electronic properties of single molecules trapped in two metal electrodes. [32,33] In the scanning tunneling microscope break junction (STM-BJ), the formation of metal-molecule-metal junctions is achieved by repeatedly moving the STM probe tip into and out of contact with the metal substrate in a solution with target molecules. The STM tip can be precisely regulated by a piezoelectric transducer.…”

Section: Single-molecule Break Junction Techniquesmentioning

confidence: 99%

Recent Advances in Photochemical Reactions on Single‐Molecule Electrical Platforms

Zhu

Zhao

et al. 2022

Macromol. Rapid Commun.

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The photochemical reaction is a very important type of chemical reaction. Visualizing and controlling photo-mediated reactions is a long-standing goal and challenge. In this regard, single-molecule electrical detection with label-free, real-time, and in situ characteristics has unique advantages in monitoring the dynamic process of photoreactions at the single-molecule level. In this review, a valuable summary of the latest process of single-molecule photochemical reactions based on single-molecule electrical platforms is provided. The single-molecule electrical detection platforms for monitoring photoreactions are displayed, including their fundamental principles, construction methods, and practical applications. The single-molecule studies of two different types of light-mediated reactions are summarized as below: i) photo-induced reactions, including reversible cyclization, conformational isomerization, and other photo-related reactions; ii) plasmon-mediated photoreactions, including reaction mechanisms and concrete examples, such as plasmon-induced photolysis of S-S/O-O bonds and tautomerization of porphycene. In addition, the prospects for future research directions and challenges in this field are also discussed.

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“…[29][30][31][32][33][34][35] As the field proceeds to explore more complex molecular structures and junction architectures and interfaces with other disciplines, researchers have started to fully unveil the hidden potential of SMJs in serving as a fertile single-molecule platform for probing physical, chemical, and biological phenomena beyond electrical conductance. [36][37][38][39] It is striking to see that some elegant experimental studies in recent years have demonstrated the possibility to drive and monitor chemical reactions, 40,41 harness the interference of electron waves, 42 achieve heat-toelectricity energy conversion, 43 manipulate electron spins, 44 and reveal detailed structural variations 45 at the single-molecule level. Noticeably, these intriguing physical and chemical effects are far beyond the original vision of using single molecules just as electronic components.…”

Section: Introductionmentioning

confidence: 99%

Beyond electrical conductance: progress and prospects in single-molecule junctions

2022

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A single-molecule blueprint for synthesis

Cited by 34 publications

References 162 publications

Surface Vacancy Generation by STM Tunneling Electrons in the Presence of Indigo Molecules on Cu(111)

Surface Vacancy Generation by STM Tunneling Electrons in the Presence of Indigo Molecules on Cu(111)

Recent Advances in Photochemical Reactions on Single‐Molecule Electrical Platforms

Beyond electrical conductance: progress and prospects in single-molecule junctions

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