Azoheteroarenes

Greenfield, Jake L.; Thawani, Aditya R.; Odaybat, Magdalena; Gibson, Rosina S. L.; Jackson, Thomas B.; Fuchter, Matthew J.

doi:10.1002/9783527827626.ch5

Cited by 13 publications

(14 citation statements)

References 97 publications

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“…A subclass of azobenzene photoswitches, the arylazopyrazoles, have shown near quantitative E to Z switching, a long-lived metastable state, and a large change in the dipole moment. − The latter feature has been recently exploited by Kimizuka and co-workers to mediate the solubility of an arylazopyrazole in aqueous media . These properties facilitate high conversions between the two isomeric forms, while their long-half-lives allow their metastable and assembled structures to be studied and deployed in applications.…”

Section: Introductionmentioning

confidence: 99%

Light Responsiveness and Assembly of Arylazopyrazole-Based Surfactants in Neat and Mixed CTAB Micelles

Tyagi

Greenfield

Jones

et al. 2022

JACS Au

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The self-assembly of an arylazopyrazole-based photosurfactant (PS), based on cetyltrimethylammonium bromide (CTAB), and its mixed micelle formation with CTAB in aqueous solution was investigated by small angle neutron and X-ray scattering (SANS/SAXS) and UV–vis absorption spectroscopy. Upon UV light exposure, PS photoisomerizes from E-PS (trans) to Z-PS (cis), which transforms oblate ellipsoidal micelles into smaller, spherical micelles with larger shell thickness. Doping PS with CTAB resulted in mixed micelle formation at all stoichiometries and conditions investigated; employing selectively deuterated PS, a monotonic variation in scattering length density and dimensions of the micellar core and shell is observed for all contrasts. The concentration- and irradiance-dependence of the E to Z configurational transition was established in both neat and mixed micelles. A liposome dye release assay establishes the enhanced efficacy of photosurfactants at membrane disruption, with E-PS exhibiting a 4-fold and Z-PS a 10-fold increase in fluorescence signal with respect to pure CTAB. Our findings pave the way for external triggering and modulation of the wide range of CTAB-based biomedical and material applications.

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Section: Introductionmentioning

confidence: 99%

Light Responsiveness and Assembly of Arylazopyrazole-Based Surfactants in Neat and Mixed CTAB Micelles

Tyagi

Greenfield

Jones

et al. 2022

JACS Au

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“…[12][13][14] These photoswitches can be serious alternatives to conventional azoarenes because of their excellent bistability, efficient photoisomerization, and tunable thermal stability of the photoswitched states (or metastable states). [15,16] Indeed, tuning their photochemical properties can be achieved through subtle structural modifications. [17] More importantly, these photoswitches provide an excellent opportunity to coordinate to the metal center through various heteroatoms.…”

Section: Introductionmentioning

confidence: 99%

Light‐Switchable Metal Complexes: Introducing Photoresponsive Behaviour Through Azoheteroarenes

et al. 2023

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Azoheteroarenes are emerging classes of photoswitches with versatile scaffolds that offer distinct features such as efficient photoisomerization, tunable stability of the photoswitched states, and bidirectional photoswitching. Moreover, the heteroatoms of such photoswitches exhibit coordination ability to bind to the metal centers. The resulting azoheteroarene‐based metal complexes can be designed and developed to tune various metal‐based properties towards intriguing applications such as in optics, magnetic properties, data storage applications, and catalysis. Despite the diverse utility of azopyridines in such contexts, other azoheteroarenes, particularly the state‐of‐the‐art five‐membered heterocycle‐based photoswitches, remain under‐explored. In this Review, we describe the diverse classes of azoheteroarene‐coordinated metal complexes reported in the literature and survey their photoswitching behaviour and applications. Furthermore, we identify potential azoheteroarene candidates for building photochrome‐coupled metal complexes and supramolecular architectures for maximizing the photo‐tuning of metal‐related properties.

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“…Functional materials that respond to external stimuli are highly sought-after for a range of applications including sensing, optoelectronic devices, mechanical actuators, and information and energy storage . Light as a stimulus is very attractive as it can be used with high spatiotemporal control and produces no waste.…”

Section: Introductionmentioning

confidence: 99%

Systematic Investigation into the Photoswitching and Thermal Properties of Arylazopyrazole-based MOF Host–Guest Complexes

Griffiths,

Greenfield,

Halcovitch

et al. 2023

Crystal Growth & Design

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A series of arylazopyrazole-loaded metal–organic frameworks were synthesized with the general formula Zn 2 (BDC) 2 (DABCO)(AAP) x (BDC = 1,4-benzenedicarboxylate; DABCO = 1,4-diazabicyclo-[2.2.2]octane; AAP = arylazopyrazole guest). The empty framework adopts a large pore tetragonal structure. Upon occlusion of the E -AAP guests, the frameworks contract to form narrow pore tetragonal structures. The extent of framework contraction is dependent on guest shapes and pendant groups and ranges between 1.5 and 5.8%. When irradiated with 365 nm light, the framework expands due to the photoisomerization of E -AAP to Z -AAP. The proportion of Z -isomer at the photostationary state varies between 19 and 57% for the AAP guests studied and appears to be limited by the framework which inhibits further isomerization once fully expanded. Interestingly, confinement within the framework significantly extends the thermal half-life of the Z -AAP isomers to a maximum of approximately 56 years. This finding provides scope for the design of photoresponsive host–guest complexes with high stability of the metastable isomer for long-duration information or energy storage applications.

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Azoheteroarenes

Cited by 13 publications

References 97 publications

Light Responsiveness and Assembly of Arylazopyrazole-Based Surfactants in Neat and Mixed CTAB Micelles

Light Responsiveness and Assembly of Arylazopyrazole-Based Surfactants in Neat and Mixed CTAB Micelles

Light‐Switchable Metal Complexes: Introducing Photoresponsive Behaviour Through Azoheteroarenes

Systematic Investigation into the Photoswitching and Thermal Properties of Arylazopyrazole-based MOF Host–Guest Complexes

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