Networking Nanoswitches for ON/OFF Control of Catalysis

Mittal, Nikita; Pramanik, Susnata; Paul, Indrajit; De, Soumen; Schmittel, Michael

doi:10.1021/jacs.6b12951

Cited by 62 publications

(40 citation statements)

References 30 publications

(55 reference statements)

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“…Formation of NetState I, represented by the 1:1 mixture of [Cu (19)] + + 18 (Fig. 27), involves the superior self-sorting of Cu + ion on nanoswitch 19 so that nanoswitch 18 remains devoid of copper(I) ion loading [66]. The follow-up transformation NetState I ?…”

Section: Double-netstate Nine-component Catalytic Machinerymentioning

confidence: 99%

Heteroleptic copper phenanthroline complexes in motion: From stand-alone devices to multi-component machinery

Goswami

Schmittel

2018

Coordination Chemistry Reviews

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a b s t r a c tTwo and a half decades of copper phenanthroline-based switches, devices and machines have illustrated the rich dynamic nature of these metal complexes. With an emphasis on the metal-ligand dissociation as the rate-determining step the present review summarizes not only spectacular examples of machinery, but also highlights rate data collected during a variety of investigations. Copper-ligand exchange reactions are mostly triggered by redox processes, addition of metal ions or addition of ligands. While the rate data spread over >8 orders of magnitude, individual effects of solvent, steric bulk, flexibility, r-basicity and the trajectory (intra-vs. intermolecular dissociation) have large impact. Unfortunately, in many cases the exact mechanism in the rate-determining step (nucleophile-induced vs. monomolecular metal-ligand dissociation) has not been determined, suggesting to invest further efforts in the physical (in)organic chemistry of such coordination-driven systems.

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Section: Double-netstate Nine-component Catalytic Machinerymentioning

confidence: 99%

Heteroleptic copper phenanthroline complexes in motion: From stand-alone devices to multi-component machinery

Goswami

Schmittel

2018

Coordination Chemistry Reviews

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“…[34] Before testing the slider-on-deck systems,weassessed the yields of the model reaction 5 + 6 + 7 for reference purposes at temperatures from 25 to 60 8 8C. After 4h,the product yields were determined by 1 HNMR spectroscopy using tetrachloroethane (TCE) as the internal standard (Figure 3).…”

mentioning

confidence: 99%

“…To probe the concept of dynamic release of the catalyst from 5·DS1,for example,wechose the prototypical conjugate addition reaction (1) of thiophenol (6)t o2 -cyclopentenone (7)w ith N-methylpyrrolidine (5)a st he catalyst (10 mol %; Figure 3). [34] Before testing the slider-on-deck systems,weassessed the yields of the model reaction 5 + 6 + 7 for reference purposes at temperatures from 25 to 60 8 8C. After 4h,the product yields were determined by 1 HNMR spectroscopy using tetrachloroethane (TCE) as the internal standard ( Figure 3).…”

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confidence: 99%

Catalytic Three‐Component Machinery: Control of Catalytic Activity by Machine Speed

et al. 2017

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Three supramolecular slider-on-deck systems DS1-DS3 were obtained as two-component aggregates from the sliders S1-S3 and deck D with its three zinc porphyrin (ZnPor) binding sites.T he binding of the two-footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two N pyr ! ZnPor interactions.A ccordingly,t he sliders move over the three zinc porphyrins in the deck at different speeds,n amely with 32.2, 220, and 440 kHz at room temperature.The addition of N-methylpyrrolidine as an organocatalyst to DS1-DS3 generates catalytic three-component machineries.B yu sing ac onjugate addition as ap robe reaction, we observed ac orrelation between the operating speed of the slider-ondeck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases,b oth the frequency of the sliding motion and the yield of the catalytic reaction increase.The connection between protein conformational dynamics and enzymatic activity has been intensely debated [1,2] because the precise spatial arrangement and high dynamics have to work together synergistically for high turnover rates in enzymes.[3] It is thus an appealing challenge to systematically use dynamic effects in artificial catalysts to speed up ap articular process. [4,5] Herein, we describe how ad ynamic slider-on-deck system can be coupled to an organocatalyst and how the sliding speed (machine speed) in this threecomponent aggregate impacts catalysis.T he results show clearly the prevalence of kinetic over thermodynamic factors in the liberation of catalyst into solution and highlight the usefulness of dynamic multicomponent machinery.Although most biological machine archetypes are multiprotein complexes,very few examples of artificial devices [6][7][8][9][10][11][12][13][14][15][16][17][18] that arise from the self-sorting of diverse components [19][20][21] have been reported, quite in contrast to the large gamut of known covalently or topologically constructed machines. [23][24][25][26][27][28][29][30][31] Forthe present study,wechose the two-component slideron-deck systems DS1-DS3 = D·(S1-S3)( Scheme 1) for the following reasons:1)InDS1-DS3,the two-footed sliders S1-S3 should move quickly on the D 3h -symmetric deck D with its three identical zinc porphyrin (ZnPor) binding sites.2 )The speed should be adjustable by changing the binding foot of S1-S3.3 )The addition of one equiv of an organocatalyst to DS1-DS3 is expected to generate the catalytic three-component machinery cat·D·(S1-S3). 4) Thes lidersf oot (various pyridine/pyrimidine derivatives:p yr) and the organocatalyst should have comparable affinity towards the binding sites of the deck, so that liberation of the catalyst into solution may be triggered by the motion of the slider. 5) Thea mount of catalyst in solution shall be quantifiable through ac atalytic process.T hereby,s ignificantly different sliding speeds in DS1-DS3 should lead to divergent yields in the catalytic reaction.B...

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“…Another use of double self-sorting has been demonstrated in examples allowing ON/OFF switching of catalysis. [46,47] Here the interdependent self-sorting, which can be regarded as a minuscule cybernetic network, comprises the two nanoswitches 31 & 32, the organocatalyst 24 and metal ions (Scheme 4). [44] The two networked states (NetStates) represent the different outcome of two self-sorting events.…”

Section: Multiple Self-sorting Events: From Structural Reorganizationmentioning

confidence: 99%

Dynamic Functional Molecular Systems: From Supramolecular Structures to Multi‐Component Machinery and to Molecular Cybernetics

Schmittel

2018

Israel Journal of Chemistry

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This essay highlights the role of single and multiple reversible self‐sorting events for the development of responsive multi‐component structures as well as multi‐state transformations, devices and machinery. Recent examples illustrate how distinct molecular devices are spatiotemporarily interconnected by chemical signaling to act as integrated machinery and highlight the enormous potential of molecular cybernetics.

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Networking Nanoswitches for ON/OFF Control of Catalysis

Cited by 62 publications

References 30 publications

Heteroleptic copper phenanthroline complexes in motion: From stand-alone devices to multi-component machinery

Heteroleptic copper phenanthroline complexes in motion: From stand-alone devices to multi-component machinery

Catalytic Three‐Component Machinery: Control of Catalytic Activity by Machine Speed

Dynamic Functional Molecular Systems: From Supramolecular Structures to Multi‐Component Machinery and to Molecular Cybernetics

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