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...

The nanoswitches 1 and 2 are interdependently linked in so-called network states (NetStates). In NetState I, defined by presence of [Cu(1)] and 2, the organocatalyst N-methylpyrrolidine catalyzes a conjugate addition. Addition of iron(II) ions as an external chemical trigger to NetState I discharges Cu from [Cu(1)]. The liberated copper(I) ion acts as a second messenger and changes the toggling state at nanoswitch 2. The resulting nanoswitch [Cu(2)] captures the catalytically active species from solution and the conjugate addition is turned OFF. Removal of the original trigger reverses the sequence and turns catalysis ON. The ON/OFF catalytic cycle was run three times in situ.

The six-component pentagon P1 with its five dynamic vertices was conceived on the basis of three different orthogonal metal complex units in a 1-fold completive self-sorting of four linear ligands and two metal ions without using directional bonding.