Molecular motor-functionalized porphyrin macrocycles

Gilissen, Pieter J.; White, Paul B.; Berrocal, José Augusto; Vanthuyne, Nicolas; Rutjes, Floris P. J. T.; Feringa, Ben L.; Elemans, Johannes A. A. W.; Nolte, Roeland J. M.

doi:10.1038/s41467-020-19123-y

Cited by 25 publications

(24 citation statements)

References 40 publications

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“…Porphyrins can have a rich redox chemistry with a variety of charging states, which might be useful for information storage in molecular junctions, 89 but might also serve as trigger to manipulate intramolecular interactions electrostatically in more complex (super)structures, paving the way towards molecular muscles and machines. 90,91 Even more visionary is the use of porphyrin based architectures as qubits integrated in a quantum computing set-up, and first porphyrin complexes with f-orbital metals such as the lanthanides Terbium and Dysprosium have already been reported. 92 However, there are structural physicochemical challenges to be faced when extended molecular architectures like e.g.…”

Section: Beta(β)-decay Values Of Molecular Porphyrin Wiresmentioning

confidence: 99%

Porphyrins as building blocks for single-molecule devices

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Section: Beta(β)-decay Values Of Molecular Porphyrin Wiresmentioning

confidence: 99%

Porphyrins as building blocks for single-molecule devices

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“…For the synthesis of the double-motorized porphyrin cage compound Zn3 (Scheme S1), we followed the same strategy as applied for the synthesis of monomotorized cage Zn2. 25 with a negative Cotton effect of the Soret band were assigned (−). The relative stereochemistry of Zn3a was identical to that of Zn2a, that is, for both compounds, the motor and Soret CD bands had the same sign.…”

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Light‐gated binding in double‐motorized porphyrin cages

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Molecular motors change conformation under the influence of light and when attached to host molecules, they may find applications as sensors and switchable catalysts. Here, we present a porphyrin macrocyclic host functionalized with two motor appendages for future catalytic applications. The compound is formed as a mixture of six stereoisomers (three sets of enantiomers), which have been separated by (chiral) chromatography. 1H NMR and chiral spectroscopy revealed that in one set of enantiomers, the two motors interact with the cavity of the host (bound‐bound), whereas in a second set, one interacts and the other one does not (bound‐loose). In the third set, both motors do not interact with the host compound (loose‐loose). The motorized hosts bind guest molecules in the order: (loose‐loose) > (bound‐loose) > (bound‐bound). They can be switched with light to pseudoidentical diastereomers, leading to orthogonal behavior in the light‐gated binding of guest molecules. Although the photoisomerization of the diastereomer set loose‐loose significantly lowers the binding affinity for viologen guests, the opposite is true for the diastereomer set bound‐bound, that is, the binding affinity increases. For the diastereomer set bound‐loose, no influence on guest binding is observed as the effect of photoisomerization on the motors is cancelled out. Key Points We present a porphyrin cage compound with two light‐switchable molecular motors for future catalytic applications The double‐motorized porphyrin cage compound is formed as a mixture of six stereoisomers (three sets of enantiomers), which could be separated, and by photoswitching converted to pseudoidentical stereoisomers The stereoisomers display different binding affinities for guest molecules, which reverse on photoswitching, leading to orthogonal guest binding behavior

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“…Zn1is an excellent host for viologen guests, which are bound in the cavity of Zn1 by a combination of electrostatic and π-stacking effects. 24 As part of a program aimed at the development of a supramolecular catalytic system that can write information on a polymeric thread we recently reported on the synthesis and properties of molecular motor-functionalized porphyrin cageZn2 , 25 which combines the rotational properties of a free molecular motor with the host-guest binding properties of the parent porphyrin cage Zn1 . Since Zn2contains only one motor substituent the two faces of the cavity of this porphyrin host are non-identical, causing ambiguity in the binding and threading process of guest molecules.…”

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“…For the synthesis of the double-motorized porphyrin cage compoundZn3 (Supporting Information, Scheme S1) we followed the same strategy as applied for the synthesis of mono-motorized cageZn2 . 25 Compound Zn3 was obtained as a mixture of six stereoisomers, i.e. three diastereomeric sets of enantiomers.…”

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“…In our previous work on single-motorized cage Zn2we showed that the chemical shifts of motor protons H-a and H-b were indicative of the presence or absence of intramolecular interactions between the naphthalene part of the motor and the cavity of the porphyrin cage. 25 The presence of such interactions in compound Zn2b was evidenced by a strong shielding effect on protons H-a and H-b , which is caused by the parallel displaced π-π stacking of the naphthalene part of the motor and the porphyrin. In contrast, this shielding effect was not present in Zn2a and also not in theC 2 -symmetric compound Zn3a , confirming their similarity.…”

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Light-gated binding in double-motorized porphyrin cages

Nolte¹,

Gilissen²,

Vanthuyne

et al. 2021

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Molecular motors change conformation under the influence of light and when attached to host molecules they may find applications as sensors and switchable catalysts. Here we present a porphyrin macrocyclic host functionalized with two motor appendages for future catalytic applications. The compound is formed as a mixture of six stereoisomers (three sets of enantiomers), which have been separated by (chiral) chromatography. 1H NMR and chiral spectroscopy revealed that in one set of diastereomers the two motors interact with the cavity of the host (bound-bound), whereas in a second set one interacts and the other one does not (bound-loose). In the third set both motors do not interact with the host compound (loose-loose). The motorized hosts bind guest molecules in the order: (loose-loose) > (bound-loose) > (bound-bound). They can be switched with light to pseudo-identical diastereomers, leading to orthogonal behavior in the light-gated binding of guest molecules. Whereas the photo-isomerization of the diastereomer set loose-loose significantly lowers the binding affinity for viologen guests, the opposite is true for the diastereomer set bound-bound, i.e. the binding affinity increases. For the diastereomer set bound-loose no influence on guest binding is observed as the effect of photoisomerization on the motors is cancelled out.

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Molecular motor-functionalized porphyrin macrocycles

Cited by 25 publications

References 40 publications

Porphyrins as building blocks for single-molecule devices

Porphyrins as building blocks for single-molecule devices

Light‐gated binding in double‐motorized porphyrin cages

Light-gated binding in double-motorized porphyrin cages

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