Photoresponsive crown ethers. 8. Azobenzenophane-type switched-on crown ethers which exhibit an all-or-nothing change in ion-binding ability

Shinkai, Seiji; Minami, Takahide; Kusano, Yumiko; Manabe, Osamu

doi:10.1021/ja00345a029

Cited by 183 publications

(61 citation statements)

References 5 publications

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“…[1][2][3] Switches based on azobenzene (Ab) have been used to control ion complexation, [4,5] electronic properties, [6] and catalysis [7] or to trigger the folding/unfolding of oligopeptide chains. [8][9][10][11][12][13] A sophisticated application of the above principle led to the preparation of chiral diarylidenes featuring a single isomerizable bond.…”

Section: In Memory Of Fernando Bernardimentioning

confidence: 99%

Quantum Chemical Modeling and Preparation of a Biomimetic Photochemical Switch

et al. 2006

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Designing and testing biomimetic switches: Multireference perturbation theory is used to model a light-driven molecular switch featuring the same photoisomerization mechanism as the chromophore of the visual pigment rhodopsin (see picture; QM/MM: quantum mechanics/molecular mechanics). By exploiting a synthetic route based on nitrilium-cation cyclization, it was shown that the designed system can indeed be prepared and characterized

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Section: In Memory Of Fernando Bernardimentioning

confidence: 99%

Quantum Chemical Modeling and Preparation of a Biomimetic Photochemical Switch

et al. 2006

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“…For instance, switches based on azobenzene have been used to control ion complexation (4,5), electronic properties (6), catalysis (7), and the folding of peptides (8)(9)(10)(11)(12)(13) whereas diarylidenes have provided the framework for the construction of rotary motors and transmissions (14). The computer modeling of switches that differ in size, polarity, and isomerization mechanism represents an attractive research target (15) yielding building blocks to be used in diverse molecular environments.…”

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confidence: 99%

An artificial molecular switch that mimics the visual pigment and completes its photocycle in picoseconds

Sinicropi

Martin

Ryazantsev

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

161

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Single molecules that act as light-energy transducers (e.g., converting the energy of a photon into atomic-level mechanical motion) are examples of minimal molecular devices. Here, we focus on a molecular switch designed by merging a conformationally locked diarylidene skeleton with a retinal-like Schiff base and capable of mimicking, in solution, different aspects of the transduction of the visual pigment Rhodopsin. Complementary ab initio multiconfigurational quantum chemistry-based computations and time-resolved spectroscopy are used to follow the light-induced isomerization of the switch in methanol. The results show that, similar to rhodopsin, the isomerization occurs on a 0.3-ps time scale and is followed by <10-ps cooling and solvation. The entire (2-photon-powered) switch cycle was traced by following the evolution of its infrared spectrum. These measurements indicate that a full cycle can be completed within 20 ps.CASPT2//CASSCF ͉ mid-IR ͉ photochemical switch ͉ time resolved spectroscopy ͉ UV-vis M olecular switches based on photochemical E/Z isomerizations have been used in different contexts to convert light energy into ''mechanical'' motion at the molecular level (1-3). For instance, switches based on azobenzene have been used to control ion complexation (4, 5), electronic properties (6), catalysis (7), and the folding of peptides (8-13) whereas diarylidenes have provided the framework for the construction of rotary motors and transmissions (14). The computer modeling of switches that differ in size, polarity, and isomerization mechanism represents an attractive research target (15) yielding building blocks to be used in diverse molecular environments. However, this cannot be limited to the computation of equilibrium properties but requires the description of the entire photocycle. In other words, one needs to compute the potential energy surfaces controlling the switch E 3 Z and Z 3 E excited-state evolution, its decay and ground state relaxation, and the competing thermal E/Z isomerization in the proper environment (e.g., in solution or in a biomolecule backbone). The complexity of these calculations impedes the study of candidates that are intractable with accurate quantum chemical methods (allowing comparison with spectroscopic data) or that feature, as for azobenzene and diarylidenes (16), more than 1 low-lying excited state, leading to a plethora of reaction paths to be computed.The retinal protonated Schiff-base chromophore of rhodopsins (17-19) constitutes an example of an E/Z switch shaped by biological evolution that can be modeled with quantitative computations (20). In bovine rhodopsin (Rh), a selective photoisomerization of the 11-cis chromophore (PSB11) occurs via evolution of a single 3 * excited state (S 1 ) that survives for only 150 fs and yields, upon decay, the all-trans ground state (S 0 ) product with a 67% quantum yield (16,20). Although these properties make Rh an excellent reference for the design of E/Z switches, irradiation of PSB11 in solution (26, 27) features an unselec...

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“…Besides a direct polymerization of suitable monomers, the subsequent attachment of azobenzenes onto polymer matrices 40,41 or the covalent attachment of polymers onto azobenzenes 42,43 has been reported. Despite the many reported methodologies, not always the expected polymers were obtained, [44][45][46] oen due to setbacks in preparation and purication.…”

Section: B30mentioning

confidence: 99%

Synthesis and characterization of new photoswitchable azobenzene-containing poly(ε-caprolactones)

et al. 2016

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A novel and efficient strategy in obtaining series of mono-and bi-armed azobenzene-containing poly(3-caprolactone)s is described, starting from a commercially available azobenzene dye via azide/alkyne-"click"-reactions. The attachment of alkyne-telechelic poly(3-caprolactone)s (1 kDa and 3 kDa), followed by chromatographic separation, allowed the attachment of either one or two PCl-chains to either side of the azobenzene-dye. The resulting mono-and bi-armed photo-switchable polymers are fully characterized by 2D-NMR techniques and show a high thermal stability. Additionally liquid chromatography at critical conditions (LCCC) coupled to ESI-TOF allowed us to prove the presence of either one or two polymer chains affixed onto the central azobenzene dye.

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Photoresponsive crown ethers. 8. Azobenzenophane-type switched-on crown ethers which exhibit an all-or-nothing change in ion-binding ability

Cited by 183 publications

References 5 publications

Quantum Chemical Modeling and Preparation of a Biomimetic Photochemical Switch

Quantum Chemical Modeling and Preparation of a Biomimetic Photochemical Switch

An artificial molecular switch that mimics the visual pigment and completes its photocycle in picoseconds

Synthesis and characterization of new photoswitchable azobenzene-containing poly(ε-caprolactones)

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