Azobased iminopyridine ligands and their rhenium metal complexes: Syntheses, spectroscopic, trans-cis photoisomerization and theoretical studies

Benmensour, Mohamed Ali; Ayadi, Awatef; Akdas-Kilig, Huriye; Boucekkine, Abdou; Fillaut, Jean‐Luc; El‐Ghayoury, Abdelkrim

doi:10.1016/j.jphotochem.2018.09.023

Cited by 10 publications

(8 citation statements)

References 26 publications

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“…NWChem was used for the quantum chemical calculation ( 48 ). Similar to literature ( 49 , 50 ), DFT calculations used the B3LYP exchange-correlation and 6-31G basis set. The solvent effect was considered by using “conductor-like screening model” (COSMO) ( 51 ).…”

Section: Methodsmentioning

confidence: 99%

Membrane-confined liquid-liquid phase separation toward artificial organelles

et al. 2021

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As the basic unit of life, cells are compartmentalized microreactors with molecularly crowded microenvironments. The quest to understand the cell origin inspires the design of synthetic analogs to mimic their functionality and structural complexity. In this work, we integrate membraneless coacervate microdroplets, a prototype of artificial organelles, into a proteinosome to build hierarchical protocells that may serve as a more realistic model of cellular organization. The protocell subcompartments can sense extracellular signals, take actions in response to these stimuli, and adapt their physicochemical behaviors. The tiered protocells are also capable of enriching biomolecular reactants within the confined organelles, thereby accelerating enzymatic reactions. The ability of signal processing inside protocells allows us to design the Boolean logic gates (NOR and NAND) using biochemical inputs. Our results highlight possible exploration of protocell-community signaling and render a flexible synthetic platform to study complex metabolic reaction networks and embodied chemical computation.

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Section: Methodsmentioning

confidence: 99%

Membrane-confined liquid-liquid phase separation toward artificial organelles

et al. 2021

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“…A major consideration is whether the intrinsic photoswitch properties can be preserved after incorporation. It is well-documented that the photoreactivity can be dramatically decreased if a photoswitch is electronically coupled to another π-conjugated unit. − To address this issue, the effect of linker structure on the strength of electronic coupling has been widely investigated, and several decoupling strategies for azobenzenes have been developed, as illustrated in Figure a. Complete decoupling can be simply achieved by inserting an sp 3 -CH group as the spacer, e.g., a methylene or an aliphatic chain, which is nonetheless not suitable for designing rigid molecular architectures.…”

Section: Introductionmentioning

confidence: 99%

(Hetero)arylazo-1,2,3-triazoles: “Clicked” Photoswitches for Versatile Functionalization and Electronic Decoupling

et al. 2021

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The development of light-responsive chemical systems often relies on the rational design and suitable incorporation of molecular photoswitches such as azobenzenes. Linking a photoswitch core with another π-conjugated molecular entity may give rise to intramolecular electronic coupling, which can dramatically impair the photoswitch function. Decoupling strategies have been developed based on additionally inserting a linker that can disrupt the throughbond electronic communication. Here we show that 1,2,3-triazolea commonly used decoupling spacercan be directly merged into the azoswitch core to construct a class of "self-decoupling" azoswitches called (hetero)arylazo-1,2,3-triazoles. Such azotriazole photoswitches are easily accessed and modularly functionalized by click chemistry. Their photoswitch property can be optimized by rational design of the substituent groups or heteroaryl rings, allowing (near-)quantitative E⇆Z photoisomerization yields and tunable Z-isomer thermal half-lives from days to years. Combined experimental and theoretical results demonstrate that the electronic structure of the photoswitch core is not substantially affected by various substituents attached to the 1,2,3-triazole unit, benefiting from its cross-conjugated nature. The combination of clickable synthesis, tunable photoswitch property, and self-decoupling ability makes (hetero)arylazo-1,2,3-triazoles intriguing molecular tools in developing photoresponsive systems with desired performance.

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“…As can be seen, upon irradiation, the isomerization occurs very quickly, ordinarily for several minutes suggested by decreasing in intensity of the band at 284 nm with the simultaneous development of another at lower wave number, 247 nm. This hypsochromic effect assigned to the π–π* transition of the cis isomer formed . The n–π* weak band moves from 456 to 407 nm with very little increase in intensity.…”

Section: Resultsmentioning

confidence: 94%

Nanoscale Coordination Polymer of Dimanganese(II) as Infinite, Flexible Nanosheets with Photo‐Switchable Morphology

Shova¹,

Vlad²,

Damoc³

et al. 2020

Eur J Inorg Chem

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An original co‐ligand association, consisting of 4,4'‐azopyridine and 1,3‐bis(carboxypropyl)tetramethyldisiloxane, is used for complexing MnII, to obtain a 2D dinuclear coordination array having infinite horizontal dimensions and nanometric thickness. Due to the shielding effect of the tetramethyldisiloxane units facing outwards on both sides, the sheets are free of any chemical or physical intermolecular interactions, as crystallographic analysis reveals. The compound shows two glass transitions, at –51 and 33 °C, and begins to decompose at 292 °C. The co‐existence in the structure of the highly hydrophobic tetramethyldisiloxane spacers and the polar metal complexed units confers amphiphilic character to the compound, making it capable of reducing the surface tension of the DMF, from 35.8 to 29.4 mN/m, at a critical micellar concentration around 1 wt.‐% complex. The presence of aggregates in solution is evidenced by dynamic light scattering. The light sensitive azopyridine units make the compound photo‐responsive. This behavior occurs both in solution as well as in the film, where the compound self‐assembles in micellar morphology when UV‐irradiated. Both conductivity and dielectric permittivity of the film increase as a result of trans–cis configuration. Magnetic measurement data indicate two antiferromagnetic coupled spins, S = 5/2, that are able to interact with small external magnetic field, i.e., during MFM scanning.

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Azobased iminopyridine ligands and their rhenium metal complexes: Syntheses, spectroscopic, trans-cis photoisomerization and theoretical studies

Cited by 10 publications

References 26 publications

Membrane-confined liquid-liquid phase separation toward artificial organelles

Membrane-confined liquid-liquid phase separation toward artificial organelles

(Hetero)arylazo-1,2,3-triazoles: “Clicked” Photoswitches for Versatile Functionalization and Electronic Decoupling

Nanoscale Coordination Polymer of Dimanganese(II) as Infinite, Flexible Nanosheets with Photo‐Switchable Morphology

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