WO2025199205A1 - Composés photosensibles - Google Patents

Composés photosensibles

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Publication number
WO2025199205A1
WO2025199205A1 PCT/US2025/020522 US2025020522W WO2025199205A1 WO 2025199205 A1 WO2025199205 A1 WO 2025199205A1 US 2025020522 W US2025020522 W US 2025020522W WO 2025199205 A1 WO2025199205 A1 WO 2025199205A1
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Prior art keywords
alkyl
membered monocyclic
bicyclic
haloalkyl
independently selected
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Inventor
Elias PICAZO
Cesar REYES
Hye Joon Lee
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University of Southern California USC
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University of Southern California USC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • DASAs donor-acceptor Stenhouse adducts
  • FIG. 1A Studies have elucidated the structure-property relationships and multi-state switching mechanism that lead to absorbance in the visible to near-IR region, negative photochromism, and significant volume and polarity changes upon switching.
  • Adaptable DASA physical properties arise from their assembly (FIG. 1B), which introduces modularity in molecular structure (FIG. 1C).
  • Second generation DASAs evaluated the donor compartment and expanded to include aromatic amine donors such as indoline (FIG. 1C). The extended conjugation provided by second generation donors decreases charge separation within the open isomer, resulting in faster switching kinetics and broader solvent compatibility. Third generation DASAs explored the acceptor compartment, and it was determined that stronger pull character leads to a bathochromic shift in absorption and better control over dark equilibria, allowing for over 95% open-to-closed isomerization upon irradiation. More recently, substitutions on the triene compartment were studied.
  • nonhydroxy triene underwent photoisomerization at either C2–C3 or C3–C4, as opposed to exclusive rotation about C2–C3 for the parent DASA (FIG. 1D).
  • Computed potential energy curves for the cyclization step point towards an energetically forbidden pathway for the nonhydroxy triene.
  • the present disclosure provides donor-acceptor Stenhouse adducts (DASAs) with heteroatom substitutions that allow for further tunability of their photoswitching properties.
  • DASAs donor-acceptor Stenhouse adducts
  • the photoresponsive compounds described herein successfully replace the hydroxyl group found on the triene moiety of previously described DASAs with other heteroatom-containing moieties, such as nitrogen- and sulfur-containing groups, allowing further tuning of the associated properties.
  • a photoresponsive compound is provided of Formula I (I) wherein all variables are as Processes for synthesizing the photoresponsive compounds described herein are also provided.
  • a process is provided for preparing a photoresponsive compound of Formula I, .
  • the reacting a compound of Formula II Attorney Docket No.11760-002WO1 R1 with a donor D-H to form the I; wherein all variables are as further defined herein.
  • Methods of using the photoresponsive compounds described herein are further provided.
  • a method is provided for changing the color and other physical properties of a material, wherein the material comprises a photoresponsive compound described herein.
  • the method comprises irradiating the material with light of a first wavelength.
  • the photoresponsive compound upon irradiation with the light, converts into a compound of Formula III: .
  • FIGs.1A-1E provide a comparative overview of donor-acceptor Stenhouse adducts generally and those particularly described in the examples herein.
  • FIG.1A Isomerization of the donor- acceptor Stenhouse adduct 1 to 1′ upon the absorbance of visible light and its thermal reversion.
  • FIG. 1B Knoevenagel condensation of 2-furaldehyde with a carbon acid acceptor, followed by furan ring opening with an amine donor to form DASA compounds.
  • FIG. 1C Synthetic advances of DASA structure per compartment.
  • FIG. 1D Vital backbone hydroxy group for Attorney Docket No.11760-002WO1 DASA composition highlighted by failure to undergo 4 ⁇ -electrocyclization with non-hydroxy triene equivalent.
  • FIG.1E Development of amino DASAs by leveraging nitrogen’s additional bonding orbital to promote a pyrrole-opening rearrangement.
  • FIG. 2A Amino DASA synthetic route, pyrrole-based aza-Piancatelli rearrangement optimization by inductive activation, and characterization of 6e by single crystal X-ray diffraction. Yields shown are representative of the aza-Piancatelli rearrangement.
  • FIG. 1D Vital backbone hydroxy group for Attorney Docket No.11760-002WO1 DASA composition highlighted by failure to undergo 4 ⁇ -electrocyclization with non-hydroxy triene equivalent.
  • FIG.1E Development of amino DASAs by
  • FIGs. 3A-3D depict the photophysical characterization of 1 st , 2 nd , and 3 rd generation DASAs as described in the examples.
  • FIG. 3A 1 st generation amino DASA 7 and hydroxy DASA 9
  • FIG.3B 2 nd generation amino DASA 6e and hydroxy DASA 10
  • FIG.3C 3 rd generation amino DASA 8 and hydroxy DASA 11. Yields are isolated yields.
  • ⁇ molar absorption coefficient in CH 2 Cl 2 .
  • FIG.3D UV-visible absorbance spectra are at 10 ⁇ M in CH 2 Cl 2 .
  • FIG. 4A-4F depict amino DASA photoisomerization and thermal reversion as described in the examples. Photoswitching comparison of 1st, 2nd, and 3rd generation amino DASAs in (FIG. 4A) CH 2 Cl 2 and (FIG. 4B) PhMe measured at their corresponding ⁇ max .
  • FIG. 4C Absorbance decrease of amino DASA 6e and absorbance increase at 381 nm in PhMe upon irradiation.
  • FIG. 4D Photoisomerization and thermal reversion of amino DASA 6e and hydroxy DASA 10 in PhMe.
  • FIG.4E Evaluation of amino DASA 6e thermal stability.
  • FIG. 4F Evaluation of hydroxy DASA 10 thermal stability.
  • FIG. 5 depicts a mechanistic comparison of DASA synthesis and photoisomerization to the aza-Piancatelli rearrangement.
  • FIGs. 6A-6B provide amino DASA 6e photophysical characterization as described in the examples.
  • FIG.6B Solvatochromic analysis was performed by obtaining the UV-visible absorption measurements of 6e in PhMe, Et 2 O, THF, EtOAc, CHCl 3 , CH 2 Cl 2 , acetone, DMSO, MeCN, and MeOH. The ⁇ max of absorbance in each solvent was plotted against the respective polarity value (ETN) using the Dimroth-Reichardt parameters.
  • ESN polarity value
  • FIGs. 7A-7B provide amino DASA 7 photophysical characterization as described in the examples.
  • FIG.7A UV-visible absorption measurements of 7 were taken at 10, 5, 1, and 0.5 ⁇ M in CH2Cl2. The ⁇ max was plotted against concentration (M).
  • FIG. 7B Solvatochromic analysis was performed by obtaining the UV-visible absorption measurements of 7 in PhMe, Et 2 O, THF, EtOAc, CHCl 3 , CH 2 Cl 2 , acetone, DMSO, MeCN, and MeOH. The ⁇ max of absorbance in each solvent was plotted against the respective polarity value (ETN) using the Dimroth-Reichardt parameters.
  • FIGs. 8A-8B provide amino DASA 8 photophysical characterization as described in the examples.
  • FIG. 8B Solvatochromic analysis was performed by obtaining the UV-visible absorption measurements of 8 in PhMe, Et2O, THF, EtOAc, CHCl3, CH2Cl2, acetone, DMSO, MeCN, and MeOH. The ⁇ max of absorbance in each solvent was plotted against the respective polarity value (ETN) using the Dimroth-Reichardt parameters.
  • FIG. 9A-9B provide hydroxy DASA 9 photophysical characterization as described in the examples.
  • FIG. 9B Solvatochromic analysis was performed by obtaining the UV-visible absorption measurements of 9 in PhMe, Et2O, THF, EtOAc, CHCl3, CH2Cl2, acetone, DMSO, MeCN, and MeOH.
  • FIGs.10A-10B provide hydroxy DASA 10 photophysical characterization as described in the examples.
  • FIGs.11A-11B provide hydroxy DASA 11 photophysical characterization as described in the examples.
  • FIG. 11A UV-visible absorption measurements of 11 were taken at 10, 5, 1, and 0.5 ⁇ M in CH2Cl2. The ⁇ max was plotted against concentration (M).
  • FIG. 11B Solvatochromic analysis was performed by obtaining the UV-visible absorption measurements of 11 in PhMe, Et2O, THF, EtOAc, CHCl 3 , CH 2 Cl 2 , acetone, DMSO, MeCN, and MeOH. The ⁇ max of absorbance in each solvent was plotted against the respective polarity value (ETN) using the Dimroth-Reichardt parameters.
  • FIGs. 12A-12D depict the solvatochromic slope comparison as described in the examples.
  • FIG.12A Charge distribution visual of linear DASA molecule.
  • FIGs. 13A-13F provide absorbance measurements of 6e during and after irradiation as described in the examples. Irradiation absorbance measurements in (FIG.13A) CH 2 Cl 2 , (FIG. 13B) PhMe, and (FIG. 13C) MeOH.
  • FIG. 15 depicts NMR in situ irradiation of 6e with narrow band 590 nm LED in CDCl3. No closed isomer was observed upon 72 hours of irradiation. No C3–C4 cis ⁇ trans isomerization was observed at –15 °C.
  • FIGs. 16A-16E provide absorbance measurements of 7 during and after irradiation as described in the examples. Irradiation absorbance measurements in (FIG.16A) CH 2 Cl 2 , (FIG. 16B) PhMe, and (FIG. 16C) MeOH.
  • FIGs. 17A-17D provide absorbance measurements of 8 during and after irradiation as described in the examples. Irradiation absorbance measurements in (FIG.17A) CH 2 Cl 2 , (FIG. 17B) PhMe, and (FIG. 17C) MeOH. Following consumption of 8 ⁇ max in the respective solvents, thermal recovery of open DASA was measured in (FIG.17D) MeOH.
  • FIGs. 18A-18F provide absorbance measurements of 9 during and after irradiation as described in the examples.
  • FIG. 18A Irradiation absorbance measurements in (FIG.18A) CH2Cl2, (FIG. 18B) PhMe, and (FIG. 18C) MeOH. Following consumption of 9 ⁇ max in the respective solvents, thermal recovery of open DASA was measured in (FIG. 18D) CH2Cl2, (FIG. 18E) PhMe, and (FIG.18F) MeOH.
  • FIGs. 19A-19F provide absorbance measurements of 10 during and after irradiation as described in the examples. Irradiation absorbance measurements in (FIG.19A) CH2Cl2, (FIG. 19B) PhMe, and (FIG. 19C) MeOH.
  • FIGs. 20A-20B provide absorbance measurements of 11 during irradiation as described in the examples. Irradiation absorbance measurements in (FIG.20A) CH2Cl2 and (FIG.20B) PhMe. Due to rapid photoswitching, accurate thermal reversion measurements could not be performed.
  • FIGs. 21A-21C depict in situ absorbance measurements in PhMe across a 10 min irradiation period. Switching comparison of 1 st (FIG. 21A), 2 nd (FIG.
  • FIGs.22A-22C depict in situ absorbance measurements in CH2Cl2 across a 10 min irradiation period. Switching comparison of 1 st (FIG. 22A), 2 nd (FIG. 22B), and 3rd generation (FIG. 22C) DASAs in CH2Cl2.
  • FIGs.23A-23C depict in situ absorbance measurements in MeOH across a 10 min irradiation period as described in the examples. Switching comparison of 1 st (FIG.23A), 2 nd (FIG.23B), and 3 rd (FIG.23C) generation DASAs in MeOH.
  • FIGs.24A-24F depict the thermal stability evaluation of DASAs as described in the examples.
  • the stability of DASAs 7 (FIG.24A), 6e (FIG.24B), 8 (FIG. 24C), 9 (FIG.24D), 10 (FIG.24E), and 11 (FIG.24F) were evaluated by absorbance decrease during 40 °C incubation periods in the absence of light. Measurements were taken at time points up until complete consumption of respective ⁇ max.
  • Absorbance measurement of 10 ⁇ M Attorney Docket No.11760-002WO1 of activated pyrrole 4e (FIG.24B) and activated furan 4fur (FIG.24F) in PhMe were plotted for comparison.
  • FIG.25 provides the 1 H NMR stack of in situ irradiation of amino DASA 6e. Over the period of 3 days, a 1.0 mg/mL solution of 6e in CDCl3 was irradiated as described in the examples. During that period, 1H NMR (600 MHz) spectra were obtained at 25 °C. After irradiating for 72 hrs, the sample was cooled to –15 °C in the NMR and the spectra was obtained at –15 °C. Notably, no significant spectroscopic changes were observed throughout the experiment or after cooling.
  • FIG.26 provides the 1 H NMR stack of in situ irradiation of hydroxy DASA 10.
  • FIG. 27 provides a Hammett value analysis of 10 and 6e as described in the examples. pKa values for 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-((4- bromophenyl)sulfonamido)benzoic acid, and 3-((4-bromophenyl)sulfonamido)benzoic acid were calculated using Advanced Chemistry Development(ACD/Labs) Software V11.02.
  • ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’.
  • the range can also be expressed as an upper limit, e.g., ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x,’ ‘about y,’ and ‘about z’ as well as the ranges of ‘less than x,’ ‘less than y.’ and ‘less than z.’
  • the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x,’ ‘about y,’ and ‘about z’ as well as the ranges of ‘greater than x,’ greater than y,’ and ‘greater than z.’
  • the phrase “about ‘x’ to ‘y’,” where ‘x’ and ‘y’ are numerical values includes “about ‘x’ to about ‘y’.”
  • Such a range format is used for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical
  • a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible isomer, e.g., each enantiomer, diastereomer, and meso compound, and a mixture of isomers, such as a racemic or scalemic mixture.
  • Attorney Docket No.11760-002WO1 Compounds described herein may contain one or more double bonds and, thus, potentially give rise to cis/trans (E/Z) isomers, as well as other conformational isomers. Unless stated to the contrary, all such possible isomers are contemplated, as well as mixtures of such isomers. Compounds described herein may also present as an equilibrium of tautomers.
  • substituted means that any one or more hydrogens on the designated atom or group are replaced with a moiety selected from the indicated group, provided that the designated atom’s normal valence is not exceeded and the resulting compound is stable.
  • a pyridyl group substituted by oxo is a pyridine.
  • a stable active compound refers to a compound that can be isolated and/or can be formulated into a form with a shelf life of at least one month.
  • a stable manufacturing intermediate or precursor to an active compound is stable if it does not degrade within the period needed for reaction or other use.
  • a stable moiety or substituent group is one that does not degrade, react, or fall apart within the period necessary for use.
  • Non-limiting examples of unstable moieties are those that combine heteroatoms in an unstable arrangement, as typically known and identifiable to those of skill in the art.
  • Any suitable group may be present on a “substituted” or “optionally substituted” position that forms a stable molecule and meets the desired purpose of the disclosure and includes, but is not limited to: halo, nitro, cyano, azido, oxo, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2- C6 alkynyl, (C3-C6 cycloalkyl)(C0-C3 alkyl)-, (3- to 8-membered monocyclic or bicyclic heterocycle)-(C0-C6 alkyl)-, (6- to 10-membered monocyclic or bicyclic aryl)-(C0-C6 alkyl)-, (5- to 10-membered monocyclic or bicyclic heteroaryl)-(C0-C6 alkyl)-, A x O-(C0-C6 alkyl)-, A x S-(C 0 -C 6 alkyl
  • a point of attachment bond denotes a bond that is a point of attachment between two chemical entities, one of which is depicted as being attached to the point of attachment bond and the other of which is not depicted as being attached to the point of attachment bond.
  • Attorney Docket No.11760-002WO1 “ ” indicates that the chemical entity “XY” is bonded to another chemical entity via attachment bond.
  • the specific point of attachment to the non-depicted entity can be specified by inference.
  • the compound CH 3 -R 3 wherein R 3 i s H or “ ,” infers that when R3 is “XY”, the point of attachment bond is the same bond as the bond by which R 3 is depicted as being bonded to CH3.
  • “Halo” or “halogen” independently indicates any fluoro, chloro, bromo or iodo.
  • nitro is represented by the formula —NO2.
  • alkyl is a straight chain or branched saturated aliphatic hydrocarbon group. In certain aspects, the alkyl is C1-C2, C1-C3, or C1-C6 (i.e., the alkyl chain can be 1, 2, 3, 4, 5, or 6 carbons in length).
  • the specified ranges, as used herein, indicate an alkyl group with a length of each member of the range described as an independent species.
  • C1-C6alkyl indicates an alkyl group having from 1, 2, 3, 4, 5, or 6 carbon atoms and is intended to mean that each of these is described as an independent species
  • C 1 -C 4 alkyl indicates an alkyl group having from 1, 2, 3, or 4 carbon atoms and is intended to mean that each of these is described as an independent species.
  • C 0 -C n alkyl is used herein in conjunction with another group, for example (C3-C7cycloalkyl)C0-C4alkyl, or -C0-C4(C3- C 7 cycloalkyl), the indicated group, in this case cycloalkyl, is either directly bound by a single covalent bond (C0alkyl), or attached by an alkyl chain, in this case 1, 2, 3, or 4 carbon atoms.
  • Alkyls can also be attached via other groups, such as heteroatoms, such as -O-C 0 -C 4 alkyl(C 3 - C7cycloalkyl).
  • alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • the alkyl group is optionally substituted as described herein.
  • Cycloalkyl is a saturated or partially unsaturated mono- or multi-cyclic hydrocarbon ring system.
  • cycloalkyl groups include cyclopropyl, Attorney Docket No.11760-002WO1 cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • the cycloalkyl group is optionally substituted as described herein.
  • Alkenyl is a straight or branched chain aliphatic hydrocarbon group having one or more carbon-carbon double bonds, each of which is independently either cis or trans, that may occur at a stable point along the chain.
  • Non-limiting examples include C2-C4alkenyl and C2-C6alkenyl (i.e., having 2, 3, 4, 5, or 6 carbons).
  • the specified ranges as used herein indicate an alkenyl group, with each member of the range described as an independent species, as described above for the alkyl moiety.
  • alkenyl include but are not limited to, ethenyl and propenyl.
  • the alkenyl group is optionally substituted as described herein.
  • Alkynyl is a straight or branched chain aliphatic hydrocarbon group having one or more carbon-carbon triple bonds that may occur at any stable point along the chain, for example, C2- C 4 alkynyl or C 2 -C 6 alkynyl (i.e., having 2, 3, 4, 5, or 6 carbons).
  • the specified ranges as used herein indicate an alkynyl group, with each member of the range described as an independent species, as described above for the alkyl moiety.
  • alkynyl examples include, but are not limited to, ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, and 5-hexynyl.
  • the alkynyl group is optionally substituted as described herein.
  • Alkoxy is an alkyl group, as defined above, covalently bound through an oxygen bridge (-O-).
  • alkoxy examples include but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, isopentoxy, neopentoxy, n-hexoxy, 2-hexoxy, 3-hexoxy, and 3-methylpentoxy.
  • an “alkylthio” or “thioalkyl” group is an alkyl group as defined above, with the indicated number of carbon atoms covalently bound through a sulfur bridge (-S-).
  • the carbonyl carbon is included in the number of carbons.
  • the alkanoyl group is optionally substituted as described herein.
  • “Aryl” indicates an aromatic group containing only carbon in the aromatic ring or rings.
  • the aryl group contains 1 to 3 separate or fused rings and is 6 to 14 or 18 ring atoms, without heteroatoms as ring members. When indicated, such aryl groups may be further substituted with carbon or non-carbon atoms or groups.
  • substitution may include fusion to a 4- to 7- or 5- to 7-membered saturated or partially unsaturated cyclic group that optionally Attorney Docket No.11760-002WO1 contains 1, 2, or 3 heteroatoms independently selected from N, O, B, P, Si and S, to form, for example, a 3,4-methylenedioxyphenyl group.
  • Aryl groups include, for example, phenyl and naphthyl, including 1-naphthyl and 2-naphthyl.
  • aryl groups are pendant.
  • An example of a pendant ring is a phenyl group substituted with a phenyl group.
  • the aryl group is optionally substituted as described herein.
  • heterocycle refers to saturated and partially saturated heteroatom-containing ring radicals, where the heteroatoms may be selected from N, O, and S.
  • the term heterocycle includes monocyclic 3-12 members rings, as well as bicyclic 5-16 membered ring systems (which can include fused, bridged, or spiro bicyclic ring systems). It does not include rings containing -O-O-, -O-S-, and -S-S- portions.
  • saturated heterocycle groups including saturated 4- to 7-membered monocyclic groups containing 1 to 4 nitrogen atoms [e.g., pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, azetidinyl, piperazinyl, and pyrazolidinyl]; saturated 4- to 6-membered monocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms [e.g., morpholinyl]; and saturated 3- to 6-membered heteromonocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms [e.g., thiazolidinyl].
  • saturated 4- to 7-membered monocyclic groups containing 1 to 4 nitrogen atoms e.g., pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, azetidinyl, piperazinyl, and pyrazolidinyl
  • partially saturated heterocycle radicals include, but are not limited to, dihydrothienyl, dihydropyranyl, dihydrofuryl, and dihydrothiazolyl.
  • partially saturated and saturated heterocycle groups include, but are not limited to, pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, pyrazolidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, thiazolidinyl, dihydrothienyl, 2,3-dihydro-benzo[1,4]dioxanyl, indolinyl, isoindolinyl, dihydrobenzothienyl, dihydrobenzofuryl, isochromanyl, chromanyl, 1,2-dihydroquinolyl, 1,2,3,4-tetrahydro-isoquinolyl, 1,2,3,4-tetrahydro-quinolyl, 2,3,4,4a,9,9,
  • Bicyclic heterocycle includes groups wherein the heterocyclic radical is fused with an aryl radical, and the point of attachment is the heterocycle ring.
  • Bicyclic heterocycle also includes heterocyclic radicals that are fused with a carbocyclic radical.
  • Representative examples include, but are not limited to, partially unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, for example, indoline and isoindoline, partially unsaturated condensed heterocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, partially unsaturated condensed heterocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms, and saturated condensed heterocyclic groups containing 1 to 2 oxygen or sulfur atoms.
  • Heteroaryl refers to a stable monocyclic, bicyclic, or multicyclic aromatic ring that contains from 1 to 4, or in some aspects 1, 2, or 3 heteroatoms selected from N, O, S, B, and P (and typically selected from N, O, and S) with remaining ring atoms being carbon, or a stable bicyclic or tricyclic system containing at least one 5, 6, or 7 membered aromatic ring which contains from 1 to 4, or in some aspects from 1 to 3 or from 1 to 2, heteroatoms selected from N, O, S, B, or P, with remaining ring atoms being carbon.
  • the only heteroatom is nitrogen.
  • the only heteroatom is oxygen.
  • the only heteroatom is sulfur.
  • Monocyclic heteroaryl groups typically have from 5 to 6 ring atoms.
  • bicyclic heteroaryl groups are 8- to 10-membered heteroaryl groups, that is groups containing 8 or 10 ring atoms in which one 5-, 6-, or 7-membered aromatic ring which contains from 1 to 4 heteroatoms selected from N, O, S, B, or P is fused to a second aromatic or non-aromatic ring, wherein the point of attachment is an aromatic ring.
  • the total number of S and O atoms in the heteroaryl ring exceeds 1, these heteroatoms are not adjacent to one another within the ring.
  • the total number of S and O atoms in the heteroaryl ring is not more than 2. In another aspect, the total number of S and O atoms in the heteroaryl ring is not more than 1.
  • heteroaryl groups include, but are not limited to, pyridinyl, imidazolyl, imidazopyridinyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl, isoxazolyl, thiazolyl, oxadiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, is
  • the term “derivative” refers to a compound having a structure derived from the structure of a parent compound (e.g., a compound disclosed herein) and whose structure is sufficiently similar to those disclosed herein and based upon that similarity would be expected by one skilled in the art to exhibit the same or similar activities and utilities as the claimed compounds, or to induce, as a precursor, the same or similar activities and utilities as the claimed compound.
  • exemplary derivatives include but are not limited to, salts, esters, amides, salts of esters or amides, and N-oxides of a parent compound.
  • a derivative is provided of a compound recited herein.
  • salts of the compounds described herein are also provided.
  • substantially pure means sufficiently homogeneous to appear free of readily detectable impurities as determined by standard methods of analysis, such as thin layer Attorney Docket No.11760-002WO1 chromatography (TLC), nuclear magnetic resonance (NMR), gel electrophoresis, high- performance liquid chromatography (HPLC) and mass spectrometry (MS), gas- chromatography mass spectrometry (GC-MS), and similar, used by those of skill in the art to assess such purity, or sufficiently pure such that further purification would not detectably alter the physical and chemical properties, such as enzymatic and biological activities, of the substance.
  • TLC thin layer Attorney Docket No.11760-002WO1 chromatography
  • NMR nuclear magnetic resonance
  • HPLC high- performance liquid chromatography
  • MS mass spectrometry
  • GC-MS gas- chromatography mass spectrometry
  • a substantially chemically pure compound may, however, be a mixture of stereoisomers.
  • Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art.
  • the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Sigma-Aldrich, (formerly MilliporeSigma, Burlington, MA) or Thermo Fisher Scientific Inc.
  • Photoresponsive Compounds The present disclosure provides photoresponsive compounds, more particularly donor-acceptor Stenhouse adducts (DASAs), which have heteroatom substitutions that allow for further tunability of their photoswitching properties.
  • DASAs donor-acceptor Stenhouse adducts
  • the photoresponsive compounds described herein successfully replace the hydroxyl group found on the triene moiety of previously described DASAs with other heteroatom-containing moieties, such as nitrogen- and sulfur-containing groups.
  • heteroatom-containing moieties such as nitrogen- and sulfur-containing groups.
  • the presence of a nitrogen-containing group on the triene moiety of a DASA allows for the inclusion of further substituents that can be varied, allowing for greater tuning of the associated physical and optical properties.
  • a photoresponsive compound of Formula I Attorney Docket No.11760-002WO1 (I) wherein: D is a donor group; X 1 is -X 2 -H, wherein X 2 is selected from: ; R 1 , R 2 , and R 3 are each independently selected from hydrogen, azido, halo, C1-C12 alkyl, C1-C12 haloalkyl, 6- to 10-membered monocyclic or bicyclic aryl, -OR 5 , and -SR 5 ; X 2a is independently selected at each occurrence from O, NR 4 , and S; R 4a is independently selected at each occurrence from R 4 , -OR 4 , -SR 4 , and -N(R 4 )(R 4 ); R 4 and R 5 are independently selected at each occurrence from hydrogen, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C2-C12 alkenyl, C2-C12 alkyny
  • R 1 is -OR 5 , wherein R 5 is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R 1 is -SR 5 .
  • R 1 is -SR 5 , wherein R 5 is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R 2 is hydrogen. In some aspects of Formula I or Formula II, R 2 is azido. In some aspects of Formula I or Formula II, R 2 is halo. In some aspects of Formula I or Formula II, R 2 is selected from fluoro, chloro, bromo, and iodo. In some aspects of Formula I or Formula II, R 2 is C1-C12 alkyl.
  • R 2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • R 2 is C1-C12 haloalkyl.
  • R 2 is selected from trifluoromethyl, trifluoroethyl, and hexafluoroisopropyl. In some aspects of Formula I or Formula II, R 2 is 6- to 10-membered monocyclic or bicyclic aryl. In some aspects of Formula I or Formula II, R 2 is selected from phenyl, 1-naphthyl, and 2-naphthyl. In some aspects of Formula I or Formula II, R 2 is -OR 5 .
  • R 2 is -OR 5 , wherein R 5 is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R 2 is -SR 5 .
  • R 2 is -SR 5 , wherein R 5 is selected from Attorney Docket No.11760-002WO1 hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R 3 is hydrogen.
  • R 3 is azido.
  • R 3 is halo.
  • R 3 is selected from fluoro, chloro, bromo, and iodo.
  • R 3 is C1-C12 alkyl. In some aspects of Formula I or Formula II, R 3 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane. In some aspects of Formula I or Formula II, R 3 is C1-C12 haloalkyl.
  • R 3 is selected from trifluoromethyl, trifluoroethyl, and hexafluoroisopropyl. In some aspects of Formula I or Formula II, R 3 is 6- to 10-membered monocyclic or bicyclic aryl. In some aspects of Formula I or Formula II, R 3 is selected from phenyl, 1-naphthyl, and 2-naphthyl. In some aspects of Formula I or Formula II, R 3 is -OR 5 .
  • R 3 is -OR 5 , wherein R 5 is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R 3 is -SR 5 .
  • R 3 is -SR 5 , wherein R 5 is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R 1 , R 2 , and R 3 are each hydrogen.
  • D may comprise any suitable donor group as known in the art to be used in the synthesis of donor-acceptor Stenhouse adducts or other photoresponsive compounds. Representative examples of such donor groups are described in, for example: US2019/0127345A1; Chem. Soc. Rev., 2018, 47, 1910-1937; and Chem. Soc. Rev., 2023, 52, 8245-8294.
  • D is selected from: ; wherein: Attorney Docket No.11760-002WO1 R 6 and R 7 are independently selected from hydrogen, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 3 -C 6 cycloalkyl)(C 0 -C 3 alkyl)-, (3- to 8-membered monocyclic or bicyclic heterocycle)-(C0-C3 alkyl)-, (6- to 10-membered monocyclic or bicyclic aryl)-(C0-C3 alkyl)-, (5- to 10-membered monocyclic or bicyclic heteroaryl)-(C 0 -C 3 alkyl)-, R z C(O)-, R z S(O)2-, R x O-C(O)-, R x S-C(O)-, (R x R y N
  • D is .
  • Attorney Docket No.11760-002WO1 R 9 and R 10 are independently hydrogen, C1-C12 alkyl, and 6- to 10-membered monocyclic or bicyclic aryl, each of which may be optionally substituted with one or more Y groups as allowed by valency;
  • R 11 and R 12 are independently selected at each occurrence from hydrogen, halo, nitro, cyano, azido, oxo, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 3 -C 12 cycloalkyl)(C0-C3 alkyl)-, (3- to 8-membered monocyclic or bicyclic heterocycle)-(C0-C3 alkyl)-, (6- to 10-membered monocyclic or bicyclic aryl
  • R 9 is hydrogen. In some of the above aspects of D, R 9 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, Attorney Docket No.11760-002WO1 2,2-dimethylbutane, and 2,3-dimethylbutane optionally substituted with one or more groups selected from Y as allowed by valency.
  • R 9 is phenyl, 1-naphthyl, and 2-naphthyl optionally substituted with one or more groups selected from Y as allowed by valency.
  • R 10 is hydrogen.
  • R 10 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane optionally substituted with one or more groups selected from Y as allowed by valency.
  • R 10 is phenyl, 1-naphthyl, and 2-naphthyl optionally substituted with one or more groups selected from Y as allowed by valency.
  • X 3 is a bond.
  • X 3 is -CH2-.
  • X 3 is -O-.
  • X 3 is -NH- or -N(alkyl or aryl)-.
  • X 4 is a bond.
  • X 4 is -CH2-.
  • X 4 is -O-. In some of the above aspects of D, X 4 is -NH- or -N(alkyl or aryl)-. Representative examples of D as may be found in Formula I include, but are not limited to: ,
  • A is selected from: ; Z 1 and Z 3 are independently selected from NR 14 and O; Z 2 is a Z 2 is a to form an arylene ring optionally substituted with one or more groups selected from Y; Z 4 is selected from CR 17 and N; X 5 , X 6 , and X 7 are independently selected from O, S, or NR 18 ; R 13 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, or 6- to 10-membered monocyclic or bicyclic aryl optionally substituted with one or more groups selected from Y; R 14 is independently selected at each occurrence from hydrogen, C1-C12 alkyl, C1-C12 haloalkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 3 -C 6 cycloalkyl)(C 0 -C 3 alkyl)-, (3- to 8-membered monocyclic
  • A is selected from: , Attorney Docket No.11760-002WO1 . C12 alkyl, or 6- to 10-membered monocyclic or bicyclic aryl.
  • Z 1 is NR 14 , wherein R 14 is hydrogen.
  • Z 1 is NR 14 , wherein R 14 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • Z 1 is NR 14 , wherein R 14 is selected from phenyl, 1-naphthyl, and 2-naphthyl. In some of the above aspects of A, Z 1 is O. In some of the above aspects of A, Z 3 is NR 14 , wherein R 14 is selected from hydrogen, C1-C12 alkyl, or 6- to 10-membered monocyclic or bicyclic aryl. In some of the above aspects of A, Z 3 is NR 14 , wherein R 14 is hydrogen.
  • Z 3 is NR 14 , wherein R 14 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • Z 3 is NR 14 , wherein R 14 is selected from phenyl, 1-naphthyl, and 2-naphthyl. In some of the above aspects of A, Z 3 is O. In some of the above aspects of A, Z 2 is a bond.
  • Z 2 is CR 15 R 16 , wherein R 15 and R 16 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, Attorney Docket No.11760-002WO1 n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane. In some of the above .
  • X 5 is NR 18 , wherein R 18 is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • R 18 is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • X 6 is O.
  • X 6 is S.
  • X 6 is NR 18 , wherein R 18 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • X 6 is NR 18 , wherein R 18 is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • R 18 is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • X 7 is O. In some of the above aspects of A, X 7 is S.
  • X 7 is NR 18 , wherein R 18 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • X 7 is NR 18 , wherein R 18 is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • R 18 is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • R 13 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • R 13 is selected from trifluoromethyl, trifluoroethyl, and hexafluoroisopropyl. In some of the above aspects of A, R 13 is selected from phenyl, 1-naphthyl, and 2-naphthyl. Representative examples of A as may be found in Formula I or Formula II include, but are not limited to: , and iodo. In some independent occurrences of Y, Y is cyano. In some independent occurrences of Y, Y is azido. In some independent occurrences of Y, Y is oxo.
  • Y is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane.
  • Y is selected from trifluoromethyl, trifluoroethyl, and hexafluoroisopropyl.
  • Y is selected from ethenyl and propenyl. In some independent occurrences of Y, Y is selected from ethynyl, propynyl, and propargyl. In some independent occurrences of Y, Y is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • Y is selected from pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, azetidinyl, piperazinyl, pyrazolidinyl, morpholinyl, tetrahydrofuranyl, tetrahydropyranyl, thiazolidinyl, indolinyl, and isoindolinyl.
  • Y is selected from phenyl, 1-naphthyl, and 2-naphthyl.
  • Y is selected from pyridinyl, imidazolyl, imidazopyridinyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl, isoxazolyl, thiazolyl, oxadiazolyl, oxazolyl, pyrrolyl, quinolinyl, isoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naph
  • Y is R x O-, wherein R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is (R x R y N)-, wherein R x and R y are independently selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R x S-C(O)-, wherein R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R x O-S(O) 2 -, wherein R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is (R x R y N)-S(O) 2 -, wherein R x and R y are independently selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z C(O)-O-, wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z C(O)-(R x N)-, wherein R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl, and wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z S(O) 2 -O-, wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z S(O) 2 -(R x N)-, wherein R x is selected from hydrogen, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl, and wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z C(O)-, wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH 2 , methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z S(O)-, wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH 2 , methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • Y is R z S(O) 2 -, wherein R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.
  • R z is selected from hydrogen, chloro, bromo, -OH, -NH2, methyl, ethyl, isopropyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phen
  • the processes described herein are performed in a polar solvent.
  • the polar solvent is a polar protic solvent.
  • the polar solvent is a fluoroalcohol, such as trifluoroethanol or hexafluoroisopropanol.
  • the polar solvent comprises hexafluoroisopropanol.
  • the process is performed in a mixture of a polar solvent and one or more additional solvents, such as dichloromethane.
  • the process may be perfomed in a mixture of hexafluoroisopropanol and dichloromethane.
  • the carbon-13 nuclear magnetic resonance shift in deuterated chloroform of the carbon labeled * in Formula II is greater than about 111 ppm wherein * corresponds to a of attachment to the remainder of the compound of Formula II.
  • D-H may comprise any suitable donor as known in the art to be used in the synthesis of donor-acceptor Stenhouse adducts or other photoresponsive compounds.
  • D-H is selected from: ;
  • D-H is selected from: H , Attorney Docket No.11760-002WO1 ; as applied to the D group in compounds of Formula I are similarly implicitly recited for the particular aspects of the donor D-H as used in the processes described herein.
  • H-A-H may comprise any suitable acceptor as known in the art to be used in the synthesis of donor-acceptor Stenhouse adducts or other photoresponsive compounds. Representative examples of such acceptors are described in, for example: US2019/0127345A1; Chem. Soc. Rev., 2018, 47, 1910-1937; and Chem. Soc. Rev., 2023, 52, 8245-8294.
  • H-A-H is selected from: as defined herein. In some aspects, H-A-H is selected from: Attorney Docket No.11760-002WO1 . group in compounds of Formula I and Formula II are similarly implicitly recited for the particular aspects of the donor H-A-H as used in the processes described herein. Representative examples of H-A-H as used in the disclosed processes include, but are not limited to: , Attorney Docket No.11760-002WO1 , the addition, subtraction, or movement of various constituents as described for each compound. Similarly, when one or more chiral centers are present in a molecule, the chirality of the molecule can be changed.
  • protecting group refers to any conventional functional group that allows one to obtain chemoselectivity in a subsequent chemical reaction. Protecting groups are described, for example, in Peter G. M. Wuts, Greene’s Protective Groups in Organic Synthesis, 5 th Ed., Wiley & Sons, 2014. For a particular compound and/or a particular chemical reaction, a person skilled in the art knows how to select and implement appropriate protecting groups and their associated synthetic methods.
  • Examples of amine protecting groups include acyl and alkoxy carbonyl groups, such as t-butoxycarbonyl (BOC) and [2-(trimethylsilyl)ethoxy]methoxy (SEM).
  • Examples of carboxyl protecting groups include C1-C6 alkoxy groups, such as methyl, ethyl, and t-butyl.
  • Examples of alcohol protecting groups include benzyl, trityl, silyl ethers, and the like.
  • Solvents can be substantially nonreactive with the starting materials (reactants), intermediates, or products under the conditions at which the reaction is carried out, i.e., temperature and pressure. Reactions can be carried out in one solvent or a mixture of more than one solvent.
  • Product or intermediate formation can be monitored according to any suitable method known in the art. For example, product formation can be monitored by spectroscopic means, such as nuclear magnetic resonance spectroscopy Attorney Docket No.11760-002WO1 (e.g., 1 H and 13 C), infrared spectroscopy, spectrophotometry (e.g., UV-visible), or mass spectrometry, or by chromatography such as high-performance liquid chromatography (HPLC) or thin layer chromatography (TLC).
  • HPLC high-performance liquid chromatography
  • TLC thin layer chromatography
  • a photoresponsive compound is provided prepared by any of the processes described herein.
  • the photoresponsive compounds described herein may find use as photoswitches.
  • Photoswitches are molecules that undergo a molecular change upon light irradiation. Upon excitation, the molecule transforms from its thermodynamically stable state to a photostationary state.
  • the molecular change may include an isomerization that modifies the photoresponsive compound's absorption spectrum, polarity, molecular volume, or geometric configuration.
  • These modifications to the photoresponsive compound may be used to control a range of properties, including, but not limited to, surface polarity, membrane permeability, surface patterning, and nanoparticle clustering.
  • these photoresponsive compounds may be formed with highly tunable absorption wavelengths, as well as tunability with respect to media and switchability in both solution and polymeric systems.
  • the photoresponsive compounds of the present disclosure may be tuned and/or modified to operate in a range of media according to any of the processes described herein.
  • the photoresponsive compounds may operate (e.g., complete or nearly complete photoswitching) in one or more of a polar medium, a non-polar medium, a solution phase medium, and a solid phase medium.
  • the photoresponsive compounds may operate in a range of solutions (e.g., solvents) and/or in a solid phase.
  • the photoresponsive compounds may operate in one or more of toluene, 1,4-dioxane, xylenes, anisole, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), water, methanol, ethanol, acetonitrile, chlorobenzene, N-methylpyrrolidone, dichlorobezene, trichlorobenzene, methylene chloride, acetone, benzene, cyclohexane, hexanes, ethyl acetate, diethyl ether, 1,2-dichloroethane, and chloroform.
  • the photoresponsive compounds may operate in a polymer matrix.
  • the photoresponsive compounds can be absorbed into the polymer matrix, incorporated through post-functionalization, or polymerized into the backbone of the polymer.
  • Polymer compositions may include one or more (methy)acrylate, (meth)acrylamide, (meth)acrylonitrile, styrene, acrylonitrile, vinyl acetate, vinylcarbazole, vinylpyridine, vinyl ether, vinyl chloride, Attorney Docket No.11760-002WO1 and siloxane monomers.
  • Other solid phase mediums which may be used may include but are not limited to, paper, nylon, and/or fibers.
  • the photoresponsive compounds can be absorbed into the medium and/or covalently attached through post-functionalization.
  • the conversion of the photoresponsive compounds may also induce a polarity change from hydrophobic to hydrophilic upon contacting electromagnetic radiation.
  • the conversion of the photoresponsive compounds may also, or in the alternative, induce a molecular change (e.g., isomerization) that can be used to convert light into mechanical work. Combined or independently, these property changes can be used to tune the photoresponsive compound's absorption spectrum, polarity, molecular volume, geometric configuration, and/or control various properties, including, but not limited to, surface polarity, surface patterning, membrane permeability, and nanoparticle clustering.
  • a temperature dependence of the thermal reversion of the photoresponsive compounds may be tuned and/or modified according to any of the processes described herein.
  • Temperature dependence can be tuned by modifying either the donor or acceptor group of the photoresponsive compounds that affects the switching kinetics of the system.
  • the substituents can be used to modify either the sterics or electronics of the system to control the switching kinetics.
  • the temperature dependence can be tuned by modifying the polymer glass transition (Tg). For example, going from a glassy to a rubbery matrix can be used to tune the kinetics of the thermal reversion, with faster reversion being observed in a rubbery matrix.
  • the photoresponsive compounds and their tunable properties provide a material particularly suited for use in applications that include, among other things, photo-responsive drug delivery, photo-responsive phase-tag system, pigment, tattoo pigment, cosmetic pigment, data storage, re-writable systems, and sensors. This shall not be construed as limiting, as the photoresponsive compounds may be used in a number of applications, either known or unknown in the art.
  • a photo-responsive drug delivery system a photo-responsive phase-tag system, pigment, a tattoo pigment, a cosmetic pigment, a data storage system, a re-writable system, a sensor, an electronic system, an energy storage system, a gas uptake and release system, a nanoreactor, a cell mimic, a liquid crystal display, an optical storage system, a photo- pharmacology system, a self-healing material, a polymer phase chemistry system, a wave- selective photo-sensing system, or a photochromic lens comprising a photoresponsive compound described herein.
  • the photoresponsive compounds described herein are for use in a photo- responsive drug delivery system, a photo-responsive phase-tag system, pigment, a tattoo pigment, a cosmetic pigment, a data storage system, a re-writable system, a sensor, an electronic system, an energy storage system, a gas uptake and release system, a nanoreactor, a cell mimic, a liquid crystal display, an optical storage system, a photo-pharmacology system, a self-healing material, a polymer phase chemistry system, a wave-selective photo-sensing system, or a photochromic lens.
  • a method is provided for changing the color of a material, wherein the material comprises a photoresponsive compound described herein.
  • a photoresponsive compound of Formula I R2 X1 (I) wherein: D is a donor group; X 1 is -X 2 -H, wherein X 2 is selected from: ; R 1 , R 2 , and R 3 are each independently selected from hydrogen, azido, halo, C1-C12 alkyl, C1-C12 haloalkyl, 6- to 10-membered monocyclic or bicyclic aryl, -OR 5 , and -SR 5 ; X 2a is independently selected at each occurrence from O, NR 4 , and S; R 4a is independently selected at each occurrence from R 4 , -OR 4 , -SR 4 , and -N(R 4 )(R 4 ); R 4 and R 5 are independently selected at each occurrence from hydrogen, C1-C12 alkyl, C1-C12 haloalkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 3 -C 6
  • Aspect 2 The photoresponsive compound of aspect 1, wherein the compound is formed from a compound of Formula II: , wherein all variables are as Aspect 3.
  • Aspect 4 The photoresponsive compound of any one of aspects 1-3, wherein X 2 is .
  • Second generation amino DASA 7 containing dialkyl amine donor isoindoline was synthesized in 43% yield and hydroxy DASA 9 was prepared in 46% yield. It should be noted that other dialkyl amines were explored but found to be incompatible with HFIP cosolvent, consistent with previous hydroxy DASA reports. No desired reactivity was observed in the absence of HFIP, pointing towards a strong dependence on the H-bond network to sufficiently polarize the C–N bond. Second generation amino DASA 6e and hydroxy counterpart 10, which contain aromatic amine donor indoline, were produced in 74% and 70% yield, respectively.
  • the bathochromic shifts from aromatic amine donors and strong carbon acid acceptors are due to more diffuse electron delocalization that decreases molecular HOMO-LUMO energetic gaps.
  • 9 to 7 has a hypsochromic shift of 42 nm, while both 10 to 6e and 11 to 8 have a shift of 37 nm.
  • the withdrawing effects of para-bromo sulfonamide can be directly contrasted to that of a hydroxyl group through Hammett value analyses.
  • First generation DASAs show that the backbone heteroatom is seemingly innocent in charge separation, providing solvatochromic slopes of – 28 nm/ETN for 7 and –29 nm/ETN for 9. However, such is not the case for second and third generation DASA photoswitches.
  • Analysis of second generation DASAs illustrates that amino DASA 6e has a greater degree of zwitterionic character, yielding a solvatochromic slope of – 11 nm/ETN, while hydroxy counterpart 10 is more neutral with a solvatochromic slope of –3 nm/ETN.
  • third generation hydroxy DASA 11 exhibits a higher degree of zwitterionic character, providing a solvatochromic slope of –54 nm/ETN compared to –45 nm/ETN for 8. Although no clear trend is established, it is apparent that the sulfonamide moiety may amplify or attenuate charge separation. This also hints at potential non-covalent interactions between the heteroatom substituent and the donor or acceptor.
  • amino DASAs enable tunability of the backbone heteroatom, allowing a direct comparison of sulfonamide- and hydroxy-substituted DASAs from each synthetic generation.
  • amino DASAs produce potential noncovalent interactions in addition to varying electronic contributions that result in a hypsochromic absorbance shift and inefficient photoswitching. It was discovered that substituting the hydroxy group for a sulfonamide moiety results in a decreased molar absorption coefficient and thermal stability, emphasizing the heteroatom’s role in efficiently stabilizing the photoswitch.
  • Triethylamine (99%) and 4- dimethylaminopyridine (99%) were obtained from Thermo Fisher Scientific.
  • Di-tert-butyl decarbonate (9%), pyridine (9%), and ethyl 4,4,4-trifluoroacetoacetate (99%) were obtained from Sigma-Aldrich.
  • Acetic acid (glacial) and acetic anhydride (99%) were obtained from Ward’s Science.4-bromobenzenesulfonyl chloride (98%) was obtained from Apollo Scientific.
  • 1-methyl-2-pyrrolecarboxaldehyde (98%) was obtained from Lancaster Synthesis Inc. Isoindoline hydrochloride (97%) was obtained from Ambeed.
  • Hexafluoro-2-propanol (99%) was obtained from Chem-Impex International. Indium (III) bromide (99%) was obtained from STREM Chemicals. Chloroform-d, methylene chloride-d 2 (99.8%), and dimethyl sulfoxide-d 6 (99.9%) were obtained from Cambridge Isotope Laboratories. Furfural, indoline, and hexafluoro-2-propanol were freshly distilled prior to use. Isoindoline was prepared from isoindoline hydrochloride by extracting isoindoline with an alkaline solution (sodium Attorney Docket No.11760-002WO1 hydroxide).
  • Reaction temperatures were controlled using IKA Plates (RCT digital) and the built-in temperature modulators.
  • Thin layer chromatography (TLC) was conducted with EMD gel 60 F254 pre-coated plates (0.25 mm) and visualized using a combination of UV light, potassium permanganate, phosphomolybdic acid, and p-anisaldehyde staining.
  • Silicycle Silica flash P60 (particle size 0.040–0.063 mm) was used for flash column chromatography.
  • 1 H NMR spectra were recorded on a Mercury (400 MHz), or Varian spectrometers (500, 600 MHz) and are reported relative to deuterated solvent signals.
  • UV- visible spectral data was collected on an Agilent Cary 5000 UV-Vis-NIR Spectrophotometer with a UV quartz 10 mm pathlength cuvette (3.5 mL). Crystallographic data was collected on a Rigaku XtaLAB Synergy-S diffractometer.
  • the crude oil was purified by flash chromatography (9.6:0.3:0.1 ⁇ 9.4:0.5:0.1 ⁇ 8.9:1.0:0.1 hexanes:EtOAc:NEt3) to provide pyrrole 2e (1.51 g, 91% yield) as a white powder.
  • compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims.
  • compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited.
  • a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

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Abstract

La présente divulgation concerne des composés photosensibles de formule I, des procédés de synthèse des composés photosensibles, ainsi que des procédés d'utilisation des composés photosensibles.
PCT/US2025/020522 2024-03-19 2025-03-19 Composés photosensibles Pending WO2025199205A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190127345A1 (en) * 2016-04-26 2019-05-02 The Regents Of The University Of California Negative photochromic materials with tunable properties
CN114573544A (zh) * 2022-03-04 2022-06-03 南京理工大学 具有多重刺激响应的分子开关及其合成方法

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Publication number Priority date Publication date Assignee Title
US20190127345A1 (en) * 2016-04-26 2019-05-02 The Regents Of The University Of California Negative photochromic materials with tunable properties
CN114573544A (zh) * 2022-03-04 2022-06-03 南京理工大学 具有多重刺激响应的分子开关及其合成方法

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CLERC MICHÈLE, SANDLASS SARA, RIFAIE-GRAHAM OMAR, PETERSON JULIE A., BRUNS NICO, READ DE ALANIZ JAVIER, BOESEL LUCIANO F.: "Visible light-responsive materials: the (photo)chemistry and applications of donor–acceptor Stenhouse adducts in polymer science", CHEMICAL SOCIETY REVIEWS, ROYAL SOCIETY OF CHEMISTRY, ENGLAND, vol. 52, no. 23, 27 November 2023 (2023-11-27), England, pages 8245 - 8294, XP093360803, ISSN: 0306-0012, DOI: 10.1039/D3CS00508A *
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