Spirothiopyran-Based Reversibly Saturable Photoresist

Vijayamohanan, Harikrishnan; Palermo, Edmund F.; Ullal, Chaitanya K.

doi:10.1021/acs.chemmater.7b00506

Cited by 31 publications

(33 citation statements)

References 38 publications

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“…To the best of our knowledge, ligation reactions of DASA photoswitches have not been reported so far and the reactivity as well as selectivity of this molecule class remain unknown. Selectively gated reactions are uncommon, with only a few successful systems known . The ability of molecules to react selectively in only one of its isomeric states is promising for the development of advanced materials, for example, for the use as inks in direct laser writing .…”

Section: Methodsmentioning

confidence: 99%

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It's a Trap: Thiol‐Michael Chemistry on a DASA Photoswitch

Alves

Wiedbrauk

Gräfe

et al. 2020

Chemistry A European J

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Donor-acceptor Stenhousea dducts( DASA) are popularp hotoswitches capable of togglingb etween two isomersd epending on the light and temperature of the system.T he cyclized polar form is accessed by visible-light irradiation, whereas the linear nonpolar form is recovered in the dark. Upon the formation of the cyclized form,t he DASA contains ad ouble bond featuring a b-carbonp rone to nucleophilica ttack.H ere, an isomer selective thiol-Michael reaction betweenthe cyclized DASA and ab ase-activated thiol is introduced. The thiol-Michael addition was carried out with an alkyl (1-butanethiol) and an aromatic thiol (p-bromothiophenol) as reaction partners, both in the presence of ab ase. Undero ptimized conditions,t he reactionp roceeds preferentially in the presenceo fl ight and base. The current study demonstrates that DASAsc an be selectively trapped in their cyclized state.Molecular photoswitches undergo reversible isomerization upon irradiation with light, and sometimes in combination with ad ifferent stimulus, for example, temperature. [1] Light, as ar eadily available and adjustable reactiont rigger,i sp articularly interesting for implementing spatiotemporal control on reaction outcomes. For example, photoswitches are employed for biomedical andb iochemical processes including targetedd rug delivery and chemical/biological sensing applications. [2][3][4][5] Photoswitches, such as derivatives of the donor-acceptor Stenhouse adduct (DASA), coexisti na ne quilibrium between two isomeric forms.O ne isomer consists of an intensely colored (blue, purple or orange)n onpolar linear form, whereas the other isomer is cyclized, polar,c olorless and commonly zwitterionic (Scheme 1). [6][7][8][9] The equilibrium between the two forms is dependent on the solvente nvironment andt he structural motifs of the DASA derivatives, consistingo fa ne lectron donor and an acceptorm oiety,r esultingi napush-pull system.U pon irradiation, the equilibrium is shifted towardst he ring cyclized isomer (cyclized form) and, upon thermalr elaxation, it returns to the initialc onjugated state (linear form). The cyclization mechanism hasbeen clarified in ac areful study by Feringa and Buma,i nw hichd ensity functional theory calculationsa nd transient absorption kinetics measurements were employed. [32] The current consensus on the cyclization processi nvolves isomerizationo ft he double bonds, followedby ab ond rotation, and finallyathermal conrotatory4 p electrocyclization leading to the cyclized ring, commonly stabilizedb yi ts zwitterionic form through ap roton transfer. [10][11][12][13] Clarification of the cyclization mechanism resulted in ap ool of DASA photoswitches bearing avariety of acceptorand donor functionalitiesaswell as an improvedk nowledge of factors influencing the switching process. [8,9,14,15] The inherent advantages of DASA photoswitches, which includesn egative photochromism, inexpensives tarting materials, modular synthesis, tunable absorption, visible-light switching, and good fatiguer esistance, are appealing for ar ...

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Section: Methodsmentioning

confidence: 99%

“…[22][23][24] The ability of molecules to react selectively in only one of its isomeric states is promising for the development of advanced materials, fore xample, for the use as inks in direct laser writing. Selectively gated reactions are uncommon, with only af ew successful systems known.…”

mentioning

confidence: 99%

It's a Trap: Thiol‐Michael Chemistry on a DASA Photoswitch

Alves

Wiedbrauk

Gräfe

et al. 2020

Chemistry A European J

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“…[104,105] Kinetic measurements combined with photokinetic simulations showed that interference lithography using conventional light sources (e.g., a green laser) on a spirothiopyran maleimide-based system delivered high-resolution features (≈45 nm lines) in thick films (tens of µm) over large areas (hundreds of µm). [106] UV-vis irradiation of some azobenzene or spiropyran-based systems induced phase transitions from solid to liquid even at temperatures close to physiological ones. [107][108][109][110][111][112][113] We should also note that photoisomerization of the spiropyran system brings the dipole moment change Δμ = 8-15 D, [104] which makes it perfect candidate for the aqueous-based photoresist.…”

Section: Optical and Deep And Extreme Ultraviolet (Duv/euv) Lithographymentioning

confidence: 99%

“…[ 104,105 ] Kinetic measurements combined with photokinetic simulations showed that interference lithography using conventional light sources (e.g., a green laser) on a spirothiopyran maleimide‐based system delivered high‐resolution features (≈45 nm lines) in thick films (tens of µm) over large areas (hundreds of µm). [ 106 ] UV–vis irradiation of some azobenzene or spiropyran‐based systems induced phase transitions from solid to liquid even at temperatures close to physiological ones. [ 107–113 ]…”

Section: Patterning Approachesmentioning

confidence: 99%

Gentle Patterning Approaches toward Compatibility with Bio‐Organic Materials and Their Environmental Aspects

Grebenko

Motovilov

Bubis

et al. 2022

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Advances in material science, bio-electronic, and implantable medicine combined with recent requests for eco-friendly materials and technologies inevitably formulate new challenges for nano-and micro-patterning techniques. Overall, the importance of creating micro and nanostructures is motivated by a large manifold of fundamental and applied properties accessible only at the nanoscale. Lithography is a crucial family of fabrication methods to create prototypes and produce devices on an industrial scale. The pure trend in the miniaturization of critical electronic semiconducting components is recently enhanced by implementing bio-organic systems in electronics. So far, significant efforts have been made to find novel lithographic approaches and develop old ones to reach compatibility with delicate bio-organic systems and minimize the impact on the environment. Herein, we briefly review such delicate materials and sophisticated patterning techniques.

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“…UV irradiation triggers the photoconversion of the SP to MC isomer, whereas green light (the "depletion" wavelength) causes the ring-closing photoisomerization of MC back to the SP form. 28 Due to the presence of a thiolate anion in the MC form, this isomer selectively and irreversibly undergoes a thiol Michael addition reaction with maleimides, to give the Michael addition product (MAP). Overall, the transformation is described as:…”

Section: Introductionmentioning

confidence: 99%