Functional Rotaxanes in Catalysis

Kwamen, Carel; Niemeyer, Jochen

doi:10.1002/chem.202002876

Cited by 75 publications

(41 citation statements)

References 93 publications

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“…Besides the use of new types of interlocked struts, one of the main objectives is to increase the structural complexity of the MIM ligands to prepare metal-organic materials having enhanced properties. For example, the utilization of interlocked catalysts [159][160][161][162][163] as ligands of MOFs would open new possibilities in heterogeneous catalysis. 11 Very likely, recent developments on the preparation of enantiopure MIMs incorporating novel chirality motifs [164][165][166] would allow significant advances in the construction of coherent chiral MOFs which can be employed in asymmetric catalysis.…”

Section: Discussionmentioning

confidence: 99%

Mechanically interlocked molecules in metal–organic frameworks

et al. 2022

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Section: Discussionmentioning

confidence: 99%

Mechanically interlocked molecules in metal–organic frameworks

et al. 2022

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“…Their stimulus–response behavior has been applied to molecular shuttles [ 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ] and molecular elevators [ 19 ] in solutions and molecular muscles in both the solid state and in solution [ 20 , 21 , 22 , 23 ]. Further applications of the rotaxanes include catalysis [ 24 , 25 , 26 , 27 , 28 ], functional polymeric materials [ 29 , 30 , 31 , 32 ], amphiphilic materials [ 33 , 34 , 35 , 36 ], and nanometal precursors [ 37 ]. Pseudorotaxanes have an axle component whose end groups are smaller than the size of the central hole of the macrocyclic component.…”

Section: Introductionmentioning

confidence: 99%

Ferrocene-Containing Pseudorotaxanes in Crystals: Aromatic Interactions with Hammett Correlation

et al. 2022

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Single crystals of pseudorotaxanes, [(FcCH2NH2CH2Ar)(DB24C8)][PF6] (DB24C8 = dibenzo[24]crown-8, Fc = Fe(C5H4)(C5H5), Ar = -C6H3-3,4-Cl2, -C6H3-3,4-F2, -C6H4-4-F, -C6H4-4-Cl, -C6H4-4-Br, -C6H3-3-F-4-Me, -C6H4-4-I) and [(FcCH2NH2CH2C6H4-4-Me)(DB24C8)][Ni(dmit)2] (dmit = 1,3-dithiole-2,4,5-dithiolate), were obtained from solutions containing DB24C8 and ferrocenylmethyl(arylmethyl)ammonium. X-ray crystallographic analyses of the pseudorotaxanes revealed that the aryl ring of the axle moiety and the catechol ring of the macrocyclic component were at close centroid distances and parallel or tilted orientation. The structures with parallel aromatic rings showed correlation of the distances between the centroids to Hammett substituent constants of the aryl groups.

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“…In fact, catenanes are promising scaffolds for catalyst developments, [42][43][44] and other aspects of MIMs such as large-amplitude co-conformational change and mechanostereochemistry have been exploited in switchable and stereoselective catalysis as well. [45][46][47][48] kinetic features of peptide backbones in enzymes (see SI Section 1). These catenane ligands can be efficiently prepared in gram-scale from the well-studied Cu(I) templated synthesis, 42,49 and they contain aliphatic linkers of different lengths for controlling the tightness of the mechanical bond.…”

Section: Introductionmentioning

confidence: 99%

Mechanical Interlocking Enhances the Electrocatalytic Oxygen Reduction Activity and Selectivity of Molecular Copper Complexes

Deng

Lai

et al. 2022

Preprint

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Efficient O2 reduction reaction (ORR) for selective H2O generation enables advanced fuel cell technology. Non-precious metal (NPM) catalysts are viable and attractive alternatives to state-of-the-art Pt-based materials that are expensive. Cu complexes inspired by Cu-containing O2 reduction enzymes in nature have yet to reach their desired ORR catalytic performance. Here, the concept of mechanical interlocking is introduced to the ligand architecture to enforce dynamic spatial restriction on the Cu coordination site unachievable using other structural means. The utility of the kinetic effects from mechanical bond in transition metal catalysis is just about to emerge, and here the catenane ligands govern the O2 adduct binding mode, thereby steering the selectivity to generate H2O as the major product via the 4e– pathway, rivaling the selectivity of Pt. The kinetic effects from the interlocked catenane ligand also promotes product elimination and boosts the onset potential by 130 mV, the mass activity by 1.8 times, and the turnover frequency (TOF) by 1.5 folds as compared to the non-interlocked counterpart. Our Cu catenane complex represents one of the first examples to take advantage of mechanical interlocking to afford electrocatalysts with enhanced activity and selectivity. The mechanistic insights gained through this integrated experimental and theoretical study are envisioned to be of practical value not just to the area of ORR energy catalysis, but also with broad implications on interlocked metal complexes that are of critical importance to the general fields in redox reactions involving proton-coupled electron transfer (PCET) steps

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Functional Rotaxanes in Catalysis

Cited by 75 publications

References 93 publications

Mechanically interlocked molecules in metal–organic frameworks

Mechanically interlocked molecules in metal–organic frameworks

Ferrocene-Containing Pseudorotaxanes in Crystals: Aromatic Interactions with Hammett Correlation

Mechanical Interlocking Enhances the Electrocatalytic Oxygen Reduction Activity and Selectivity of Molecular Copper Complexes

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