An unusual single-crystal-to-single-crystal [2 + 2] photocyclisation reaction of a TTF-arylnitrile derivative

Hayward, John; Gumbau‐Brisa, Roger; Alberola, Antonio; Clarke, Caroline S.; Rawson, Jeremy M.; Pilkington, Melanie

doi:10.1039/c4ce00346b

Cited by 4 publications

(2 citation statements)

References 69 publications

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“…Although solid-state phase transitions are not uncommon in thiazyl radical chemistry, such solid-state reactions typically occur with small net atomic displacements . More generally, other solid-state transformations, such as the topochemical [2+2] cycloaddition of alkenes, have particularly well-defined geometric requirements for such solid-to-solid reactions.…”

Section: Resultsmentioning

confidence: 99%

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC₆F₄CNSSN^•

et al. 2016

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The α-and β-phases of the thiazyl radical p-NCCFCNSSN (1) can be selectively prepared by careful control of the sublimation conditions, with the α-phase crystallizing preferentially when the substrate temperature is maintained below -10 °C, whereas the β-phase is isolated when the substrate temperature is maintained at or above ambient temperature. Differential scanning calorimatry studies reveal that the α-phase converts to the β-phase upon warming over the range 111-117 °C (ΔH = +4 kJ·mol) via a melt-recrystallization process, with the β-phase itself melting at 167-170 °C (ΔH = 27 kJ·mol). IR and Raman spectroscopy can be used to clearly discriminate between 1α and 1β. The α-phase shows a broad maximum in the magnetic susceptibility around 8 K that, coupled with a broad maximum in the heat capacity, is indicative of short-range order. Some field dependence of the susceptibility below 3 K is observed, but the lack of features in the ac susceptibility, M vs H plots, or heat capacity mitigates against long-range order in 1α.

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Section: Resultsmentioning

confidence: 99%

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC₆F₄CNSSN^•

et al. 2016

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“…Despite the numerous examples of TTF-based complexes and framework materials that fulfil these criteria, only five examples of complexes have been crystallographically shown to undergo photo-dimerisation, all of which occur on only one side of the TTF core [31][32][33][34][35] . The ability for this material to undergo double photocyclisation likely arises from the framework providing geometrical constraints to fulfill Schmidt's criteria, while also exhibiting flexibility to respond to the structural change.…”

Section: Synthesismentioning

confidence: 99%

Reversible single crystal-to-single crystal double [2+2] cycloaddition induces multifunctional photo-mechano-electrochemical properties in framework materials

et al. 2020

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Reversible structural transformations of porous coordination frameworks in response to external stimuli such as light, electrical potential, guest inclusion or pressure, amongst others, have been the subject of intense interest for applications in sensing, switching and molecular separations. Here we report a coordination framework based on an electroactive tetrathiafulvalene exhibiting a reversible single crystal-to-single crystal double [2 + 2] photocyclisation, leading to profound differences in the electrochemical, optical and mechanical properties of the material upon light irradiation. Electrochemical and in situ spectroelectrochemical measurements, in combination with in situ light-irradiated Raman spectroscopy and atomic force microscopy, revealed the variable mechanical properties of the framework that were supported using Density Functional Theory calculations. The reversible structural transformation points towards a plethora of potential applications for coordination frameworks in photo-mechanical and photoelectrochemical devices, such as light-driven actuators and photo-valves for targeted drug delivery.

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Five-Membered Ring Systems

Aitken¹,

Dragomir²

2015

Progress in Heterocyclic Chemistry

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An unusual single-crystal-to-single-crystal [2 + 2] photocyclisation reaction of a TTF-arylnitrile derivative

Abstract: Irradiation of single crystals of a benzonitrile substituted tetrathiafulvalene with polychromatic light results in a [2 + 2] cycloaddition reaction.

Cited by 4 publications

References 69 publications

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC₆F₄CNSSN^•

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC₆F₄CNSSN^•

Reversible single crystal-to-single crystal double [2+2] cycloaddition induces multifunctional photo-mechano-electrochemical properties in framework materials

Five-Membered Ring Systems

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An unusual single-crystal-to-single-crystal [2 + 2] photocyclisation reaction of a TTF-arylnitrile derivative

Abstract: Irradiation of single crystals of a benzonitrile substituted tetrathiafulvalene with polychromatic light results in a [2 + 2] cycloaddition reaction.

Cited by 4 publications

References 69 publications

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC6F4CNSSN•

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC6F4CNSSN•

Reversible single crystal-to-single crystal double [2+2] cycloaddition induces multifunctional photo-mechano-electrochemical properties in framework materials

Five-Membered Ring Systems

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Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC₆F₄CNSSN^•

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC₆F₄CNSSN^•