scholarly journals Mechanochemically Gated Photoswitching: Expanding the Scope of Polymer Mechanochromism

Synlett ◽  
2019 ◽  
Vol 30 (15) ◽  
pp. 1725-1732 ◽  
Author(s):  
Ross W. Barber ◽  
Molly E. McFadden ◽  
Xiaoran Hu ◽  
Maxwell J. Robb

Mechanophores are molecules that undergo productive, covalent chemical transformations in response to mechanical force. Over the last decade, a variety of mechanochromic mechanophores have been developed that enable the direct visualization of stress in polymers and polymeric materials through changes in color and chemiluminescence. The recent introduction of mechanochemically gated photoswitching extends the repertoire of polymer mechanochromism by decoupling the mechanical activation from the visible response, enabling the mechanical history of polymers to be recorded and read on-demand using light. Here, we discuss advances in mechanochromic mechanophores and present our design of a cyclopentadiene–maleimide Diels–Alder adduct that undergoes a force-induced retro-[4+2] cycloaddition reaction to reveal a latent diarylethene photoswitch. Following mechanical activation, UV light converts the colorless diarylethene molecule into the colored isomer via a 6π-electrocyclic ring-closing reaction. Mechanically gated photoswitching expands on the fruitful developments in mechanochromic polymers and provides a promising platform for further innovation in materials applications including stress sensing, patterning, and information storage.1 Introduction to Polymer Mechanochemistry2 Mechanochromic Reactions for Stress Sensing3 Regiochemical Effects on Mechanophore Activation4 Mechanochemically Gated Photoswitching5 Conclusions

2019 ◽  
Vol 31 (5) ◽  
pp. 997-1001
Author(s):  
V. Chitra ◽  
D. Roopsingh

A new series of four photo-crosslinkable thermotropic liquid crystalline poly(ester amides) were synthesized by direct polycondensation of 2,5-pyridine dicarboxylic acid with two different varying diols and diamines. Two diamines employed in the synthesis were 4,4′-diaminodiphenyl methane and 1,4-diaminobenzene. The arylidene diols 2,5-bis(4-hydroxy-3-methoxybenzylidene)cyclopentanone and 2,6-bis(4-hydroxy-3-methoxybenzylidene)cyclohexanone were also used. The synthesized poly(ester amides) were characterized by qualitative solubility test, FT-IR, 1H and 13C NMR spectra. The monomeric moieties were found to be well incorporated in the polymer back bone. The molecular weight of the polymer was assessed by gel permeation chromatography (GPC). The thermal phase transition behavior and liquid crystallinity of the poly(ester amides) were investigated by differential thermogravimetry (DTG) and hot stage optical polarized microscopy (HOPM), respectively. Interestingly, these poly(ester amides) in dimethylacetamide were found to possess photo-crosslinking characteristics when irradiated by UV light. These polymeric materials may find utility value in optical information storage devices.


2019 ◽  
Vol 16 (6) ◽  
pp. 527-543 ◽  
Author(s):  
Pedro M.E. Mancini ◽  
Carla M. Ormachea ◽  
María N. Kneeteman

During the last twenty years, our research group has been working with aromatic nitrosubstituted compounds acting as electrophiles in Polar Diels-Alder (P-DA) reactions with different dienes of diverse nucleophilicity. In this type of reaction, after the cycloaddition reaction, the nitrated compounds obtained as the [4+2] cycloadducts suffer cis-extrusion with the loss of nitrous acid and a subsequent aromatization. In this form, the reaction results are irreversible. On the other hand, the microwave-assisted controlled heating become a powerful tool in organic synthesis as it makes the reaction mixture undergo heating by a combination of thermal effects, dipolar polarization and ionic conduction. As the Diels-Alder (D-A) reaction is one of the most important process in organic synthesis, the microwave (MW) irradiation was applied instead of conventional heating, and this resulted in better yields and shorter reaction times. Several substituted heterocyclic compounds were used as electrophiles and different dienes as nucleophiles. Two experimental situations are involved: one in the presence of Protic Ionic Liquids (PILs) as solvent and the other under solvent-free conditions. The analysis is based on experimental data and theoretical calculations.


1997 ◽  
Vol 52 (7) ◽  
pp. 851-858 ◽  
Author(s):  
Gunther Seitz ◽  
Johanna Siegl

The anomeric imido esters 5 and 6, appropriate precursors for C-nucleoside synthesis, were prepared and utilized as heterodienophiles in a Diels-Alder reaction with inverse electron demand to yield the novel, protected 1.2.4-triazine C-nucleosides 8 and 9. They could be deprotected by treatment with 70% trifluoroacetic acid to furnish the free C-nucleosides 10 and 11. The triazine „aglycon“ of 8 contains an electron deficient diazadiene system, highly activated to react with various electron rich dienophiles such as enamines, enol ethers and several cyclic ketene acetals in an „inverse“ [4+2]-cycloaddition reaction. The Diels-Alder adducts spontaneously eliminate N2 and after follow-up reactions the O-TBDPS protected pyridine-C-nucleosides 13, 15, 17,19, 21 and 23 are formed. Removal of the protecting group by treatment with CF3CO2H /H2O leads to the corresponding 2’,3’-dideoxy-β-D-ribofuranosyl- pyridines.


2021 ◽  
Author(s):  
Razvan Cioc ◽  
Tom Smak ◽  
Marc Crockatt ◽  
Jan Kees Van der Waal ◽  
Pieter C A Bruijnincx

The furan Diels-Alder (DA) cycloaddition reaction has become an important tool in green chemistry, being central to the sustainable synthesis of many chemical building blocks. The restriction to electron-rich furans...


Materials ◽  
2021 ◽  
Vol 14 (5) ◽  
pp. 1080
Author(s):  
Clever Aparecido Valentin ◽  
Marcelo Kobelnik ◽  
Yara Barbosa Franco ◽  
Fernando Luiz Lavoie ◽  
Jefferson Lins da Silva ◽  
...  

The use of polymeric materials such as geosynthetics in infrastructure works has been increasing over the last decades, as they bring down costs and provide long-term benefits. However, the aging of polymers raises the question of its long-term durability and for this reason researchers have been studying a sort of techniques to search for the required renewal time. This paper examined a commercial polypropylene (PP) nonwoven geotextile before and after 500 h and 1000 h exposure to ultraviolet (UV) light by performing laboratory accelerated ultraviolet-aging tests. The state of the polymeric material after UV exposure was studied through a wide set of tests, including mechanical and physical tests and thermoanalytical tests and scanning electron microscopy analysis. The calorimetric evaluations (DSC) showed distinct behaviors in sample melting points, attributed to the UV radiation effect on the aged samples. Furthermore, after exposure, the samples presented low thermal stability in the thermomechanical analysis (TMA), with a continuing decrease in their thicknesses. The tensile tests showed an increase in material stiffness after exposition. This study demonstrates that UV aging has effects on the properties of the polypropylene polymer.


1995 ◽  
Vol 50 (2) ◽  
pp. 189-195 ◽  
Author(s):  
Andreas Karst ◽  
Burkhardt Broschk ◽  
Joseph Grobe ◽  
Duc Le Van

Reaction of the cyclotetraphosphane (PCF3)4 or of a mixture of (PCF3)4 and (PCF3)5 with 2,3-dimethyl-1,3-butadiene or isoprene at 25 °C leads to the [4 + 2]-cycloadducts of bis(trifluoromethyl) diphosphene and the phospholene derivatives 2a and 2b, respectively, in the molar ratio diphosphinine/phospholene = 1/2. The analogous reactions of the cycloarsanes (AsCF3)4,5 give the Diels/Alder compounds 4 and 5 of bis(trifluoromethyl)diarsene in 90% yield without arsolene formation. Cyclopentadiene, 1,3-cyclohexadiene and cis or trans piperylene do not react with (AsCF3)4,5, up to temperatures of 60 °C. However, the corresponding [4 + 2]-cycloadducts 6 - 8 are produced by irradiation of the reaction mixture with UV light. The novel phospholenes 2a and 2b as well as the diarsinines 4 - 8 have been characterized by spectroscopic data (MS, NMR, IR). 2a was coordinated as a phosphane ligand to the pentacarbonylchromium fragment by reaction with the photochemically generated complex Cr(CO)5 · THF to afford the new compound (3).


2021 ◽  
Author(s):  
Gibu George ◽  
Anton J Stasyuk ◽  
Miquel Solà

The Diels-Alder cycloaddition reaction between 1,3-cyclohexadiene and a series of C60 fullerenes with encapsulated (super)alkali/(super)halogen species (Li+@C60, Li2F+@C60, Cl-@C60, and LiF2-@C60) was explored by means of DFT calculations. Reactivity of...


Sign in / Sign up

Export Citation Format

Share Document