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HomeChemistryExact electrical gating of the single-molecule Mizoroki-Heck response

Exact electrical gating of the single-molecule Mizoroki-Heck response


System fabrication and characterisation

The palladium-catalysed Mizoroki–Heck response is broadly utilized in natural synthesis due to its strong skill to assemble C–C bonds. By choosing correct catalyst molecules, the Mizoroki–Heck response is powerful and insensitive to air and moisture, which reveals wonderful tolerance to various response environments. We selected the Mizoroki–Heck response because the mannequin response to discover gate-tuning catalysis on single-molecule units. The kernel of the bridge molecule, an N-heterocyclic carbene-palladium (NHC–Pd) complicated, is flexible and environment friendly in cross-coupling reactions22, in addition to the Mizoroki–Heck response23. We synthesised the bridge molecule and covalently linked it between two graphene level electrodes to kind secure Graphene-Molecule-Graphene Single-Molecule Junctions (GMG-SMJs)24 (Fig. 1a, extra artificial particulars are introduced in Supplementary Word 1 and Supplementary Figs. 115). The profitable connection of bridge molecules may very well be decided by the response of present–voltage (IV) curves (Fig. 1b). With optimised circumstances, roughly 17% with ~16 of 92 units on the identical silicon chip confirmed responsive present modifications alongside voltage variation (Supplementary Fig. 16).

Fig. 1: Preparation and characterisation of a single-molecule catalyst gadget.
figure 1

a Schematic of a single-molecule gadget for the Mizoroki–Heck response. Black ball: carbon atom in graphene; brown ball: carbon atom within the molecular bridge; crimson ball: oxygen atom within the molecular bridge; darkish blue ball: nitrogen atom within the molecular bridge; inexperienced ball: palladium atom within the molecular bridge; white ball: carbon atom derived from bromobenzene; purple ball: bromine atom in bromobenzene; gray ball: carbon atom derived from styrene. b IV curves earlier than and after preparation of the single-molecule gadget. The voltage response indicated the profitable preparation of the single-molecule gadget. c Fluorescent super-resolution imaging of the single-molecule catalyst in the course of the Mizoroki–Heck response between 3-bromoperylene and styrene. A 405 nm, 5 mW laser was targeted on the graphene gadget by way of a ×100 oil lens with 5000 photographs taken with an publicity time of fifty ms. d The excitation mild and 300 mV bias voltages have been utilized concurrently at 298 Ok, and the real-time fluorescent sign of the single-molecule web site was in contrast with the monitored present sign by way of the only molecule. e Normalised fluorescence emission spectra of 3-bromoperylene and its Mizoroki–Heck response product in macroscopic experiments. f Fluorescent spectroscopies recorded on the single-catalyst response web site. DBU 1,5-diazabicyclo(5,4,0)undec-5-ene, DMF N,N-dimethylformamide.

To verify that just one molecule was linked between the electrodes, the stochastic optical reconstruction microscopy (STORM with single-molecule decision25) impact in the course of the Mizoroki–Heck response was investigated. These difficult experiments have been carried out on the self-built tremendous high-resolution optical-electrical built-in platform (Supplementary Fig. 17), and realised by utilizing styrene and fluorescent 3-bromoperylene as response substrates beneath primary circumstances. The successive Mizoroki–Heck response catalysed by the kernel of the GMG-SMJ induced blinking on the catalytic web site due to the nonradiative vitality/cost switch from the catalytic centre to graphene electrodes. The ensuing single-molecule-resolution fluorescence picture (Fig. 1c and Supplementary Fig. 18) confirmed that just one molecule was linked between the electrodes. Moreover, the synchronisation of the recorded optical and electrical sign modifications exhibited the traits of the single-molecule response course of and additional confirmed the single-molecule conjunction (Fig. 1d and Supplementary Film 1). Then, the single-molecule web site was targeted and the fluorescence emission spectra have been recorded in the course of the response. After the addition of styrene to the essential resolution of 3-bromoperylene for five h, the broadening of the height with an extended wavelength within the fluorescence emission spectrum was noticed (Fig. 1f). Compared with the macroscopic fluorescence emission spectra of 3-bromoperylene and its cross-coupling product (Fig. 1e), and in additional mixture with the macroscopic experiment of the Mizoroki–Heck cross-coupling response (extra particulars and dialogue are introduced in Supplementary Notes 1 and 2) and the present stage transformation (as mentioned beneath, Fig. 2), we concluded that the linked single molecule can catalyse the Mizoroki–Heck response. What’s left unclear, nevertheless, is how a slight blue shift of the height with a shorter wavelength happens whether or not it’s by way of photobleaching of the cross-coupling product or one other associative mechanism.

Fig. 2: Electrical monitoring and sign attribution to the task of the single-molecule Mizoroki–Heck response.
figure 2

a Present sign variations with a bias voltage of 300 mV between supply and drain electrodes within the Mizoroki–Heck response circumstances at 298 Ok (left), and corresponding frequency distributions of the present indicators (proper). Inset: enlarged frequency distribution of the present stage II. Response circumstances: 1 mM PhBr, 1 mM styrene and 1 mM DBU in DMF. b Three modes of the present stage transformation in a. c The connection and reversibility of the present ranges by way of statistics. d The Mizoroki–Heck catalytic cycle and the attribution to the task of various present ranges. e The change of the present stage after the addition of DBU to the initially linked molecule (left) and frequency distributions of the present indicators in the course of the Mizoroki–Heck response (proper). Inset: enlarged frequency distribution of the present stage II. f The change of the present stage after the addition of PhBr to the ensuing construction from e (with out DBU, left) and frequency distributions of the present indicators in the course of the Mizoroki–Heck response (proper). Inset: enlarged frequency distribution of the present stage II. g The change of the present stage after the addition of extra styrene to the ensuing construction from f (left) and frequency distributions of the present indicators in the course of the Mizoroki–Heck response (proper). Inset: enlarged frequency distribution of the present stage II. h The change of the present stage after the addition of 1-bromo-2-(3-methylbut-3-en-1-yl)benzene to the ensuing Pd(0) intermediate (one other single-molecule gadget, left) and frequency distributions of the present indicators in the course of the reductive Mizoroki–Heck response (proper). Inset: enlarged frequency distribution of the present stage II.

Visualisation of the Mizoroki–Heck response

To visualise the Mizoroki–Heck response course of and elucidate a complete mechanism, electrical monitoring with excessive decision (nA stage for present and ~17 μs for time) was carried out, and the connection between electrical present ranges and the construction of the bridge molecule was elucidated. A N,N-dimethylformamide (DMF) resolution of bromobenzene, styrene, and 1,5-diazabicyclo(5,4,0)undec-5-ene (DBU) was added right into a home-made response cell, which encircled the bridge molecule on the gadget. After making use of a 0.3 V bias voltage between two graphene electrodes, common periodic present modifications together with the time (Fig. 2a, left) have been monitored, indicating the development of the catalytic cycle of the Mizoroki–Heck response. The modifications in present ranges suggest the transformation of the constructions throughout the linked single molecule, and the dwell time of a sure present stage corresponds to the residence time of a comparatively secure intermediate in the course of the response. We then utilised machine studying to analyse the quantity and worth of present ranges (Supplementary Fig. 19). The values fell into 4 present ranges (Fig. 2a, proper), representing 4 detectable intermediates in the course of the Mizoroki–Heck response. The 4 present ranges have been marked as present ranges I, II, III and IV, respectively, from low to excessive. Determine 2b particulars an enlarged sample of a number of present stage transformations. To search out out the regularity of the transformation, we additional utilised programmes to analyse the time trajectories of the 4 present ranges (extra particulars are introduced in Supplementary Word 3 and Supplementary Software program 1). The transformation processes have been introduced by way of statistics ranging from present stage I (which was attributed to the sign of an NHC–Pd(0) complicated vide infra). Determine 2c confirmed the connection and reversibility of the present ranges (Supplementary Fig. 20 for extra particulars). The outcomes indicated that intermediates associated to present ranges I and III may very well be reworked reversibly, in addition to III and IV. In distinction, intermediates associated to present ranges IV and II confirmed irreversible transformation, in addition to II and I. It may very well be inferred that {the electrical} Mizoroki–Heck transformation sequence was I→III→IV→II→I periodically. These outcomes have been useful in assigning the constructions of various present ranges in accordance with the mechanism of the Mizoroki–Heck response (Fig. 2nd).

Additional intermediate-control reactions (Fig. 2e–h and Supplementary Figs. 2124) and theoretical calculations (Fig. 3a and Supplementary Figs. 2532) have been carried out to help these attributions to assignments. The transformation of the present ranges indicated synchronous modifications within the GMG-SMJ construction. When the bottom resolution (DBU in DMF) was added to the response cell containing a newly fabricated single NHC–Pd complicated, the present dropped to ~6 nA (Fig. 2e, left), which was in keeping with present stage I throughout the monitored Mizoroki–Heck response (Fig. 2e, proper and extra particulars in Supplementary Fig. 21). In keeping with earlier experiences26, the change after including DBU ought to correspond to the pre-activation course of and formation of the Pd(0) intermediate. Subsequently, present stage I must be attributed to the Pd(0) intermediate, and this attribution to the task will be additional verified by experiments with completely different halobenzenes (Supplementary Fig. 33). Within the following step, the DBU resolution was eliminated and washed, adopted by addition of a bromobenzene (PhBr) resolution. The present elevated to ~22 nA (Fig. 2f, left), which was in keeping with present stage III (Fig. 2f, proper and extra particulars in Supplementary Fig. 21), and present stage III must be attributed to the oxidative addition intermediate26. Subsequently, the styrene resolution was added to the cell, and the present dropped barely to ~20 nA (Fig. 2g, left), which was in keeping with present stage II (Fig. 2g, proper and extra particulars in Supplementary Fig. 21). Present stage II ought to correspond to the intermediate after the oxidative addition intermediate throughout the Mizoroki–Heck catalytic cycle (Fig. 2nd). Subsequently, present stage II was attributed to the olefin insertion intermediate. This attribution to the task will be verified by the response between the Pd(0) intermediate and 1-bromo-2-(3-methylbut-3-en-1-yl)benzene (Fig. 2h), and the response would keep on the olefin insertion intermediate due to the shortage of β-H27. Whereas triethylamine (as reductant) was added, the reductive Mizoroki–Heck response of 1-bromo-2-(3-methylbut-3-en-1-yl)benzene would occur27, and the present stage involving the particular substrate (Fig. 2h, left) was in keeping with present stage II throughout the reductive Mizoroki–Heck response (Fig. 2h, proper and extra particulars in Supplementary Fig. 22). Moreover, the addition of hydrogen bromide (HBr) and (E)−1,2-diphenylethene to the Pd(0) intermediate28,29 resulted within the present stage II, which additionally helps the attribution to the task of present stage II (Supplementary Fig. 23). Lastly, though the olefin coordination intermediate was not detected by way of the stepwise-addition reactions, the attribution to the task of olefin coordination intermediate will be achieved conveniently by inspecting the response trajectories (Fig. 2b, c). Subsequently, present stage IV was attributed to the olefin coordination intermediate (Supplementary Fig. 24).

Fig. 3: Theoretical free vitality floor calculation and experimental kinetics of the single-molecule Mizoroki–Heck response.
figure 3

a Theoretical free vitality floor calculation. IPr 1,3-bis(2,6-diisopropylphenyl)−1H-imidazol-3-ium-2-ide, TS transition state, INT intermediate. b The only-molecule Mizoroki–Heck response beneath completely different temperatures (left) and the corresponding attribution to the task of the 4 present ranges (proper). Inset: detected transformations of the present ranges. Response circumstances: 1 mM PhBr, 1 mM styrene and 1 mM DBU in DMF. c Price constants for every elementary response at varied temperatures. The error scales have been derived from the corresponding single exponential fittings of the dwell instances (Supplementary Fig. 36). d Arrhenius plots of the ahead and reverse reactions. The activation energies of the ahead and reverse reactions have been obtained by suits of the speed constants on the varied temperatures utilizing the method: ln(ok) = ln A − Ea/(R × 1000) × (1000/T), A: pre-exponential issue. The error scales have been derived from the corresponding single exponential fittings of the dwell instances (Supplementary Fig. 36).

The theoretical calculation outcomes additionally show the accuracy of the attributions to assignments. DFT calculations point out that the intermediates of Pd(0), oxidative addition, olefin coordination and olefin insertion are comparatively secure (Fig. 3a and Supplementary Fig. 25). Below primary circumstances, the β-H elimination intermediate is troublesome to dwell to seize due to the low vitality barrier and the consumption of HBr by DBU. The very best vitality barrier is the reverse technique of olefin insertion (contemplating each ahead and reverse processes), which is in step with the reversibility evaluation mentioned above (Fig. 2c and Supplementary Fig. 20h). Furthermore, these attributions to assignments are in step with the theoretical simulation of the transmission spectra and IV curves (Supplementary Figs. 31 and 32). Collectively, all these outcomes persistently help the attributions to assignments proven in Fig. 2nd.

The only-molecule gadget can tolerate completely different temperatures, permitting us to check each thermodynamics and kinetics of reactions. We carried out the Mizoroki–Heck response at 5 completely different temperatures (298, 288, 278, 268 and 258 Ok), and the indicators are introduced in Fig. 3b (left) (extra temperature-dependent measurements are introduced in Supplementary Figs. 3437). After idealising the It curves (Supplementary Fig. 35), detailed kinetics inside Mizoroki–Heck catalytic cycle have been analysed. The dwell instances (τ) of various detectable intermediates are longer at decreased temperatures (Fig. 3b, proper and Supplementary Fig. 36). Particularly, at room temperature (298 Ok), the dwell instances of the 4 intermediates are 6.1 ± 0.2 ms (Pd(0)), 4.8 ± 0.6 ms (oxidative addition), 3.0 ± 0.6 ms (olefin coordination) and three.2 ± 0.4 × 10−1 ms (olefin insertion), respectively. The only elementary-reaction fee and its fixed will be obtained by way of ok = r = 1/<τ> (approximated as a zero-order response at 1 mM in accordance with our earlier work30, Fig. 3c, Supplementary Fig. 37 and Supplementary Tables 1 and 2). The oxidative addition course of may very well be reversible when sterically cumbersome ligands have been launched31, and our measurements confirmed a comparable reversible course of within the single-molecule response circumstances the place cumbersome NHC ligands are utilized (Fig. 2b, center). As well as, the coordination of olefin was additionally reversible (Fig. 2b, proper), which is in settlement with the earlier experiences32. Nevertheless, the insertion of olefin was irreversible, and it may very well be attributed to the thermodynamically unfavourable reverse technique of olefin insertion (β-carbon elimination of the insertion product, Fig. 3a) and the steric hindrance. The transformation between the olefin insertion intermediate and the Pd(0) intermediate was additionally irreversible on this response system, which concerned two major steps, β-hydride elimination and reductive elimination/dissociation of the Mizoroki–Heck product. Subsequently, the irreversibility may very well be defined by its non-elementary-reaction course of and the low vitality barrier of the ahead processes, in addition to the consumption of HBr by DBU. Briefly, this platform allows the investigation of the basic course of within the catalytic Mizoroki–Heck response, particularly for olefin insertion and β-hydride elimination/product forming steps which are unimaginable to differentiate by standard strategies33. Moreover, the activation energies of those processes have been calculated primarily based on the Arrhenius equation (Fig. 3d). In addition to the experimental activation vitality values, the kinetic parameters (free vitality of activation, enthalpy of activation and entropy of activation) and thermodynamic parameters (free vitality change, enthalpy change and entropy change) have been additionally obtained quantitatively (Supplementary Desk 3), which aren’t accessible in earlier research beneath in situ response circumstances for the Mizoroki–Heck response, demonstrating the aptitude of our methodology.

Gate tuning of the single-molecule Mizoroki–Heck response

With the above leads to hand, we then investigated single-molecule gate-tuning catalysis. The tuning impact will be visualised or deduced conveniently with assistance from {the electrical} single-molecule platform. The gate electrode was launched to the units, and an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) was employed because the response solvent for its skill to ship an electrical subject by way of the formation of an electrical double layer (Fig. 4a, b). Completely different gate voltages have been utilized with a continuing bias voltage (VD = 0.3 V), and the present indicators of the Mizoroki–Heck response have been monitored and recorded (Supplementary Fig. 38).

Fig. 4: Molecular orbital gating in a single-molecule gadget.
figure 4

a Schematic of a single-molecule gadget with an ionic liquid gate electrode (linked with a distant steel gate electrode) for the Mizoroki–Heck response. Ionic liquid: 1-butyl-3-methylimidazolium tetrafluoroborate. b {Photograph} of an actual gadget with steel gate electrodes. Inset: enlarged space of the gadget. c IV curves measured for various values of VG primarily based on a Pd(0) GMG-SMJ. d Fowler–Nordheim plots comparable to the IV curves in c. The arrows point out the boundaries between transport regimes (comparable to Vtrans). e Linear match of Vtrans versus VG. α: gate effectivity issue. The error scales have been derived from the statistics of 4 completely different units. f Energetic diagram of the alignment of molecular orbitals relative to the graphene Fermi stage in Pd(0) single-molecule transistors beneath completely different gate voltages. Efficient molecular orbital gating vitality, eVG,eff = e│αVG. LUMO lowest unoccupied molecular orbital, HOMO highest occupied molecular orbital.

Present ranges representing the intermediates within the Mizoroki–Heck response modified because the gate voltage was different (Supplementary Fig. 39), which manifests that the FMOs of the wired molecules have been tuned. The management of FMOs may additionally be mirrored by experimentally observable ionisation energies and electron affinities by way of Koopmans’ Theorem34. It was additionally discovered that the relative present values concerning the 4 intermediates beneath a sure gate voltage remained mounted. To have a transparent view of the vitality offset between the contact Fermi stage and the closest molecular stage liable for cost transport, the transition voltage (Vtrans) was analysed. When a destructive gate voltage was utilized, the tunnelling present by way of GMG-SMJs was enhanced, whereas a constructive gate voltage suppressed the present (Fig. 4c). Subsequent, the Fowler–Nordheim plots of ln(I/V2) versus 1/V have been educed (Fig. 4d), in addition to Vtrans versus VG for the GMG-SMJ (Fig. 4e). The constructive signal of α = (1.1 ± 0.0) × 10−1 within the GMG-SMJ explicitly signifies that HOMO-mediated tunnelling serves because the dominant transport channel. Moreover, the molecular orbital shift produced by the utilized gate voltage will be additionally analysed quantitatively by way of an efficient molecular orbital gating vitality, eVG,eff = e│αVG (Fig. 4f). Because the gate voltage diminished from the constructive to the destructive, the HOMO stage of the molecular bridge rose energetically and shifted near the Fermi stage. These electrical traits of the GMG-SMJ demonstrated molecular orbital gating by way of our single-molecule platform, which is a harbinger for the helpful response regulation described beneath.

Significantly, when the gate voltages are intense sufficient, the entire Mizoroki–Heck catalytic cycle will be suppressed. At a −2.0 V gate voltage, the intermediate, NHC–Pd(0), couldn’t be monitored, suggesting the blocked catalytic cycle (Fig. 5a, proper). At a +2.0 V gate voltage, solely the present stage of Pd(0) intermediate was noticed, which meant the lack of the catalytic reactivity (Fig. 5b, proper). Word that the catalytic course of can proceed easily with out gate voltages (Fig. 2a). Particularly, the Mizoroki–Heck response will be switched on or off by gate tuning. {The electrical} single-molecule platform can not solely current the standing of a sure response, but additionally present extra particulars beneath the off standing which is often ignored. The off standing beneath a −2.0 V gate voltage nonetheless includes the response restricted to transformations amongst intermediates of oxidative addition, olefin coordination and olefin insertion. This “hidden” info signifies that the bizarre reverse response between the olefin coordination intermediate and the olefin insertion intermediate beneath gate tuning might present a complementary avenue for C–C bond activation, which affords a direct method to modifying molecular scaffolds35,36. To display the practicability of gate-tuning on-off of the Mizoroki–Heck response, various gate voltages of 0 and −2 V (or 0V and +2 V), have been utilized to the response combination, and instantaneous begin or cease of the Mizoroki–Heck response was noticed (Fig. 5a, b, left). The gate voltages will be utilized at any time, which signifies that exact temporal management of the Mizoroki–Heck response is on the market. Subsequently, {the electrical} gating of single-molecule catalysis has nice potential specifically functions, for instance, 3D printing (to set off or terminate a response at an arbitrary time). Along with switching the response on and off with freedom, it may be utilised to design new modes of single-molecule FETs and catalytic reactions.

Fig. 5: Gate tuning of the single-molecule Mizoroki–Heck response.
figure 5

Response circumstances: 1 mM PhBr, 1 mM styrene and 1 mM DBU in ionic liquid. a Gate-control on/off of the Mizoroki–Heck response by way of making use of −2 V/0 V gate voltage (left) and the affect of −2 V gate voltage on the catalytic cycle (proper). NHC N-heterocyclic carbene. b Gate-control on/off of the Mizoroki–Heck response by way of making use of +2 V/0 V gate voltage (left) and the affect of +2 V gate voltage on the catalytic cycle (proper). c The tuning impact of the entire Mizoroki–Heck response beneath completely different gate voltages. The outcomes have been calculated by counting the catalytic cycles in 4 5-s intervals (Supplementary Figs. 4245). The error scales have been derived from the statistics of 4 completely different units. d The tuning impact of oxidative addition course of (response between Pd(0) and bromobenzene) and its reverse course of. The error scales have been derived from the corresponding single exponential fittings of the dwell instances (Supplementary Fig. 40).

To realize a deeper perception into this electrical gating, the kinetics of the Mizoroki–Heck response beneath completely different gate voltages have been calculated and analysed (Supplementary Figs. 40 and 41). Firstly, the Mizoroki–Heck catalysis will be promoted distinctly beneath sure gate voltages (Fig. 5c). For instance, the turnover frequency (TOF) can rise to three.0 ± 0.2 s−1 beneath −0.6 V as compared with the TOF of response with out gating, 2.2 ± 0.3 s−1 (the TOF values have been calculated primarily based on a number of units of gate-voltage-dependent experiments, Supplementary Figs. 4245). The promotion of a Mizoroki–Heck response beneath gate voltages outcomes from the decrement of the vitality barrier of olefin insertion (rate-determining step) inside a sure vary of gate voltages (Supplementary Figs. 2628). Secondly, the elementary steps throughout the catalytic cycle can be influenced markedly. The oxidative addition course of is dominated by the reactivity of the catalyst for sure substrates. Extra electron-donating ligands on the transition steel catalyst will facilitate the oxidative addition course of, whereas comparatively electron-poor catalysts have a tendency to advertise the reductive elimination course of. The catalyst’s reactivity in direction of oxidative addition will be tuned by electrical fields derived from double layers of ionic liquid when gate voltages are utilized. When the destructive gate voltages have been extra intensive, the speed of the oxidative addition course of turned quicker; when the constructive gate voltages have been greater, the speed of the Pd(0) regeneration was quicker (Fig. 5d). These laws originate from the tuning of the FMOs throughout the NHC–Pd complicated by way of gating, which results in the completely different reactivities of the linked catalyst for oxidative addition or reductive elimination (Supplementary Fig. 29). Such a tuning impact elucidates the capability of the oriented electrical subject on the modulation of oxidative addition course of, which was beforehand investigated by an in depth computational research37 and an experimental work primarily based on scanning tunnelling microscope-based break junctions38. Moreover, the gating voltages additionally affect olefin coordination, olefin insertion, β-H elimination and reductive elimination, and all the results on the elementary steps end result within the promotion or suppression of the entire Mizoroki–Heck response (Fig. 5c and Supplementary Figs. 2730 and 41). All these kinetic outcomes of the Mizoroki–Heck response above current the highly effective functionality of single-molecule gate tuning, which supplies a technique for tuning the reactivity of catalysts with a continuing catalyst molecule and may function a mannequin platform to visualise the affect of oriented exterior electrical fields (EEFs). This platform additionally has the potential to determine reactions with ambiguous intermediates and uncover new reactivities with electrical gating.

In abstract, facilitated by high-resolution single-molecule electrical detection, the dynamics of a Mizoroki–Heck response have been deciphered, together with the visualisation of the response trajectory, the detection of hidden intermediates and the quantification of the kinetics of every elementary step throughout the Mizoroki–Heck response. The research of extremely reactive olefin insertion intermediates and associated elementary-reaction kinetics beneath catalytic circumstances have been realised, which comprehensively illuminates the Mizoroki–Heck catalytic cycle. Extra importantly, a gate electrode was launched to the single-molecule electrical detection platform and unprecedented gate-controllable single-molecule catalysis has been realised. The reactivity for each the entire catalytic cycle and elementary steps will be tuned exactly by way of electrostatic gating, which presents nice potentials within the utility of spatially and temporally controllable chemical processes, FET-based singe-molecule catalysis and catalysis beneath oriented EEFs.

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