Search results for "Isomerization"

Excited-state non-radiative decay in stilbenoid compounds: An: Ab initio quantum-chemistry study on size and substituent effects

2019

In the framework of optoelectronic luminescent materials, non-radiative decay mechanisms are relevant to interpret efficiency losses. These radiationless processes are herein studied theoretically for a series of stilbenoid derivatives, including distyrylbenzene (DSB) and cyano-substituted distyrylbenzene (DCS) molecules in vacuo. Given the difficulties of excited-state reaction path determinations, a simplified computational strategy is defined based on the exploration of the potential energy surfaces (PES) along the elongation, twisting, and pyramidalization of the vinyl bonds. For such exploration, density functional theory (DFT), time-dependent (TD)DFT, and complete-active-space self-co…

Nanocatalysts for High Selectivity Enyne Cyclization: Oxidative Surface Reorganization of Gold Sub-2-nm Nanoparticle Networks

2021

International audience; Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization–Diels–Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensor…

Photoresponsive Halogen-Bonded Liquid Crystals: The Role of Aromatic Fluorine Substitution

2019

A new strategy for controlling the liquid crystalline and photophysical properties of supramolecular mesogens assembled via halogen bonding is reported. Changing the degree of fluorination at the halogen-bond donor of the supramolecular liquid crystal allows for the fine-tuning of the halogen bond strength and thereby provides control over the temperature range of the mesophase. At least three fluorine atoms have to be present to ensure efficient polarization of the halogen-bond donor and the formation of a mesophase. In addition, it was found that stilbazole acceptors are superior to their azopyridine counterparts in promoting stable liquid crystalline phases. The halogen-bond-driven supra…

Highly Robust but Surface-Active: N-Heterocyclic Carbene-Stabilized Au25 Nanocluster as a Homogeneous Catalyst

2019

<div> <div> <div> <p>Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Herein, we report a novel N-heterocyclic carbine-stabilized Au25 nanocluster with high thermal and air stabilities as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25(iPr2-bimy)10Br7]2+ (iPr2-bimy=diisopropyl-benzilidazolium) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2- bimyAuBr with NaBH4 in o…

Photo-switching in a hybrid material made of magnetic layered double hydroxides intercalated with azobenzene molecules.

2014

Financial support from the EU (Projects HINTS FP7-263104-2 and SpinMol Advanced Grant ERC-2009-AdG-20090325), the Spanish Ministerio de Economia y Competitividad (Projects with FEDER cofinancing MAT 2009-14528-C02-01, MAT2011-22785, MAT2012-38567-C02-01, CTQ-2011-26507, Consolider-Ingenio in Molecular Nanoscience CSD2007-00010, Consolider-Ingenio 2010-Multicat CSD2009-00050, and Severo Ochoa Program SEV-2012-0267), Generalitat Valenciana (PROMETEO and ISIC-Nano programs), and VLC/Campus Microcluster "Functional Nanomaterials and Nanodevices" is gratefully acknowledged. C. M. G. thanks the Spanish MINECO for a Ramon y Cajal Fellowship (RYC-2012-10894). We also acknowledge P. Atienzar and J. …

Photoresponsive anisotropic and isotropic gels of semicarbazide-azobenzene organogelators: the use of magnetic polymer colloids to detect gel-sol tra…

2020

Photoinduced gel-sol transformation of semicarbazide-azobenzene-based organogels containing entrapped organic solvents (isotropic gel) and liquid-crystalline material (anisotropic gel) has been studied. Thin films (4 µm) of gel materials were used to study the gel-sol transformation, as thicker films possess high absorbance due to the relatively high concentration of the gelator molecules. Photoinduced trans-cis isomerization of the azobenzene units causes destruction of the gel structure, and the consequent change in viscosity has been investigated employing magnetic polymer colloids. In the gel state the movement of the colloids is restricted due to their entrapment within the gel fibers …

Cover Feature: Tuneable Emission of Polyhedral Oligomeric Silsesquioxane Based Nanostructures that Self‐Assemble in the Presence of Europium(III) Ion…

2020

A New Opto-dielectric Effect Based on the Photoisomerization of Azo Compounds in Ferroelectric Liquid Crystals

1995

Reversible Modulation of Elasticity in Fluoroazobenzene-Containing Hydrogels Using Green and Blue Light.

2017

Hydrogels are soft materials that have found multiple applications in biomedicine and represent a good platform for the introduction of molecular switches and synthetic machines into macromolecular networks. Tuning their mechanical properties reversibly with light is appealing for a variety of advanced applications and has been demonstrated in the past; however, their activation typically requires the use of UV light, which displays several drawbacks related to its damaging character and limited penetration in tissues and materials. This study circumvents this limitation by introducing all-visible ortho-fluoroazobenzene switches into a hydrophilic network, which, as a result, can be activat…

Spin Crossover Metal-Organic Frameworks with Inserted Photoactive Guests: On the Quest to Control the Spin State by Photoisomerization

2021

International audience; Three Hofmann-like metal-organic frameworks {Fe(bpac)[Pt(CN)4]}•G (bpac=1,2-bis(4-pyridyl)acetylene) were synthesized with photoisomerizable guest molecules (G = trans-azobenzene, trans-stilbene or cis-stilbene) and were characterized by elemental analysis, thermogravimetry and powder X-ray diffraction. The insertion of guest molecules and their conformation were inferred from Raman and FTIR spectra and from single-crystal X-ray diffraction and confronted with computational simulation. The magnetic and photomagnetic behaviors of the framework are significantly altered by the different guest molecules and different conformations. On the other hand, photoisomerization …