Topochemical photo-reversible polymerization of a bioinspired monomer and its recovery and repolymerization after photo-depolymerization

Johnston, Priscilla; Braybrook, Carl; Saito, Kei

doi:10.1039/c2sc20380d

Cited by 57 publications

(78 citation statements)

References 47 publications

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“…Structure investigations of partially polymerized structures are rare and often restricted to a single intermediate state (Grimm et al, 1982;Albouy et al, 1983). Even rarer is work regarding depolymerization (Johnston et al, 2012). To the best of our knowledge, there has been no extensive structural and kinetic study of 2DPs with similar detail to the studies on 1DPs.…”

Section: Previous Workmentioning

confidence: 99%

Unraveling two-dimensional polymerization in the single crystal

et al. 2018

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Two-dimensional single-crystal-to-single-crystal polymerization and depolymerization are described in detail. The results are based on in-house and synchrotron X-ray diffraction experiments conducted on several samples at 100 K and room temperature. The reactions are associated with considerable molecular motions of all components (monomer, template and incorporated solvent molecules), which can be as large as 1 Å . Continuous polymerization leads to a gradual gap opening between the emerging two-dimensional polymer layers, which allows for increased mobility of the solvent molecules. The positional flexibility of both the solvents and the weakly bound templates buffers the local strain induced by polymerization through a complex chain of movements. As a consequence, the accumulated global strain remains small enough to essentially preserve the single-crystalline state in the course of a complete polymerization/depolymerization cycle. The unit-cell parameters evolve in an unusual way. The a and c axes of the trigonal lattice slightly increase during polymerization, even though van der Waals interactions are replaced by shorter covalent bonds and the involved molecules shrink. However, the c axis experiences a significant drop of more than 1 Å during the first depolymerization step. Progressive depolymerization expands the c axis again, but it does not quite reach the value of the fresh crystal. These effects can be explained by local strain formation and compensation mechanisms and by annealing effects during heat-induced depolymerization. An interesting side effect of the polymerization is the reorientation of incorporated solvent molecules, which give the crystal a tunable dipole moment. Of particular importance for the understanding of two-dimensional polymers is the evolution of the connectivity between molecules during polymerization and depolymerization. Combining reaction kinetics with structural information, such as the polymerization-induced displacement of reactive sites, allowed for the development of a propagation model, in which both polymerization and depolymerization proceed in a self-impeding fashion. This model is supported by Monte Carlo simulations. research papers J. Appl. Cryst. (2018). 51, 481-497 Gregor Hofer et al. Two-dimensional polymerization in the single crystal 483 research papers J. Appl. Cryst. (2018). 51, 481-497 Gregor Hofer et al. Two-dimensional polymerization in the single crystal 485 research papers J. Appl. Cryst. (2018). 51, 481-497 Gregor Hofer et al. Two-dimensional polymerization in the single crystal 495 Figure 14(a) Graphical representation of the average anthracene-anthracene distance between M S and M T . (b) Change of the average anthracene-anthracene distance between M S and M T upon polymerization.

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Section: Previous Workmentioning

confidence: 99%

Unraveling two-dimensional polymerization in the single crystal

et al. 2018

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“…[50][51][52] As a consequence, previously reported polymerization reactions induced by photocycloadditions only occurred efficiently in the crystalline state upon precise alignment via crystal engineering. 53,54 We propose that the polymerization reaction described here proceeds efficiently for two reasons: (i) the combination of large aromatic systems with a polar PEG linker lead to a prearrangement of the styrylpyrene units in THF, favored by dispersion interactions between the large aromatic systems. (ii) The relatively low photon energies of the applied wavelengths (>430 nm) prevent non-specic photodamage of the reactive groups and polymeric backbone.…”

Section: Photopolymerizationmentioning

confidence: 99%

Wavelength-gated photoreversible polymerization and topology control

et al. 2020

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“…Photodimerization is an interesting photoreversible reaction for its applications as photoresists, self‐healing materials, nanocarriers, and responsive polymers . In addition, dimerizations can be considered green chemistry reactions because photons do not leave residues and reactions can take place at room temperature and even in the solid state …”

Section: Light Adaptive Gatesmentioning

confidence: 99%

Light‐Responsive Polymer Membranes

Pantuso

Filpo

Nicoletta

2019

Advanced Optical Materials

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Stimuli‐responsive polymer membranes have gained particular attention for the ability to tune opportunely their physicochemical properties under the application of an external stimulus. Heat, pH value, ionic strength, pressure, humidity, electric and magnetic fields, antigen/antibody interactions, chemical reactions, and light can be used as triggers for specific responses in polymer membranes. In particular, light is a fascinating stimulus, as it is a green energy, which can be modulated in a precise and convenient way. In addition, it allows remote and contactless interactions without changing the original chemical environment. This review reports recent progresses in light‐responsive polymer membranes with particular attention to chemical groups and responsive mechanisms.

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Topochemical photo-reversible polymerization of a bioinspired monomer and its recovery and repolymerization after photo-depolymerization

Cited by 57 publications

References 47 publications

Unraveling two-dimensional polymerization in the single crystal

Unraveling two-dimensional polymerization in the single crystal

Wavelength-gated photoreversible polymerization and topology control

Light‐Responsive Polymer Membranes

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