Stereoregular hybrid azobenzene-cyclosiloxanes with photoinduced reversible solid to liquid transition properties

DOI: 10.1016/j.jphotochem.2020.113033

Source and publish data:

Journal of Photochemistry and Photobiology A: Chemistry (2021)

Update date:2022-08-11

Topics:

Authors:

Bakirov, Artem

Buzin, Mikhail

Cherkaev, Georgij

Migulin, Dmitry

Shchegolikhina, Olga

Vysochinskaya, Yulia

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1016/j.jphotochem.2020.113033

A new type of stereoregular hybrid azobenzene-organocyclosiloxane discrete molecular structures with photoactive azobenzene groups unidirectionally connected to rigid cyclosiloxane frames through alkyl spacers of different lengths were developed for the first time. The kinetics and thermodynamics of nondegradative reversible trans-cis photoisomerization processes of the synthesized azobenzene-cyclosiloxane conjugates investigated using UV/Vis spectroscopy, DSC and XRD methods showed dependency on their molecular structures. It has been observed that room temperature UV (365 nm) irradiation of the synthesized hybrids leads to photoliquefaction effect consisting of a photoinduced phase transition of crystal solids into liquids. The photoliquefaction process was observed and confirmed with DSC, XRD and POM methods. Backward solidification process was generated with visible light and by heating. The tetra-azobenzene substituted cyclosiloxane single molecule compounds described in this work can be regarded as promising candidates for the development of new hybrid smart materials with many potential high-tech applications.

Full text of DOI:10.1016/j.jphotochem.2020.113033

Journal of Photochemistry & Photobiology, A: Chemistry 407 (2021) 113033

Contents lists available at ScienceDirect

Journal of Photochemistry & Photobiology, A: Chemistry

journal homepage: www.elsevier.com/locate/jphotochem

Stereoregular hybrid azobenzene-cyclosiloxanes with photoinduced

reversible solid to liquid transition properties

Dmitry Migulin^a*, Yulia Vysochinskaya^{a b}, Mikhail Buzin^b, Artem Bakirov^a

Georgij Cherkaev^a, Olga Shchegolikhina^a

^aN.S. Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, 117393 Moscow, Profsoyuznaya st. 70, Russia

^bA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Vavilova st. 28, Russia

^cNational Research Centre “Kurchatov Institute”, Akademika Kurchatova pl., 1, 123182, Moscow, Russia

A R T I C L E I N F O

A B S T R A C T

Keywords:

A new type of stereoregular hybrid azobenzene-organocyclosiloxane discrete molecular structures with photo-

active azobenzene groups unidirectionally connected to rigid cyclosiloxane frames through alkyl spacers of

different lengths were developed for the ﬁrst time.

Azobenzene

Stereoregular

Cyclosiloxane

Photoliquefaction

Trans-cis isomerization

The kinetics and thermodynamics of nondegradative reversible trans-cis photoisomerization processes of the

synthesized azobenzene-cyclosiloxane conjugates investigated using UV/Vis spectroscopy, DSC and XRD

methods showed dependency on their molecular structures.

It has been observed that room temperature UV (365 nm) irradiation of the synthesized hybrids leads to

photoliquefaction effect consisting of a photoinduced phase transition of crystal solids into liquids. The photo-

liquefaction process was observed and conﬁrmed with DSC, XRD and POM methods. Backward solidiﬁcation

process was generated with visible light and by heating.

The tetra-azobenzene substituted cyclosiloxane single molecule compounds described in this work can be

regarded as promising candidates for the development of new hybrid smart materials with many potential high-

tech applications.

1. Introduction

photocontrolled switchable adhesives, lithography photoresists [2],

solar thermal fuels [3] have been published.

Photoresponsive compounds with azobenzene units capable of

reversible trans–cis photoisomerization transitions leading to changes in

molecular conﬁgurations have been a subject of increased interest for a

long time because of potential applications of such substances in a vast

array of high-tech applications, such as optical and electronic switching,

information storage, and use in construction of non-linear optical and

photoactuator devices [1].

The photoliquefaction effect was observed both for azobenzene

polymers and for single molecule azo-compounds. It was estimated that

for polymers with side-chain azobenzene moieties reversible solid to

liquid phase transformations [4] proceed due to changes in polymers

glass transition temperatures when their azo- groups undergo trans-cis

photoisomerization transition. At the same timefor highly ordered

crystalline solid single molecule azo-compounds the photoliquefaction

process is based on the crystal-to-melt ﬁrst order phase transition but

due to the insufﬁcient molecular free volume bulk photoisomerization in

this type of compoundsis often suppressed and therefore that only a

limited number of azo-functionalized single molecule structures have

been reported to be capable of undergoing a photoliquefaction process

under certain conditions [5,6].

Some azobenzene-containing compounds are known to have unique

transition properties from solid to liquid state when trans-cis photo-

isomerization occurs. Though the phenomenon of athermal photo-

liquefaction has known for quite some time, it has been somewhat

neglected for several decades [2] until recently, when an interest to-

wards new azobenzene developed materials capable of photoinduced

reversible solid-to-liquid phase transitions due to their many potential

high-tech applications has grown signiﬁcantly and a number of in-

vestigations dedicated to azobenzene based healable coatings,

One example of the room temperature single molecule photo-

liquefaction effect was observed for multi-azobenzene functionalized

sugar alcohol scaffolds [5]. While the photoliquefaction effect was

* Corresponding author.

E-mail address: migulinda@ispm.ru (D. Migulin).

https://doi.org/10.1016/j.jphotochem.2020.113033

Received 13 August 2020; Received in revised form 10 October 2020; Accepted 5 November 2020

Pellentesque rhoncus tempor nisl, at porttitor ipsum suscipit quis. Proin mattis, urna id ultricies volutpat, augue dui

scelerisque purus, et tristique libero justo sed quam. Class aptent taciti sociosqu ad litora torquent per conubia nostra, per

inceptos himenaeos. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.

Vestibulum ipsum arcu, cursus nec commodo eget, egestas vel dui. Donec vulputate nec orci

Lorem ipsum dolor sit amet, consectetur adipiscing elit. Aliquam tempor aliquet risus, nec auctor ante ultrices vel. Nam

rutrum justo quis magna ornare, non lobortis purus faucibus. In hac habitasse platea dictumst. Vivamus imperdiet est vel

massa fringilla fringilla. Curabitur eros nulla, ornare quis sollicitudin ac, accumsan in tellus. Mauris tempus efficitur mi et

scelerisque. Duis diam arcu, facilisis vel eleifend vitae, congue eu nulla

Pellentesque rhoncus tempor nisl, at porttitor ipsum suscipit quis. Proin mattis, urna id ultricies volutpat, augue dui

scelerisque purus, et tristique libero justo sed quam. Class aptent taciti sociosqu ad litora torquent per conubia nostra, per

inceptos himenaeos. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.

Vestibulum ipsum arcu, cursus nec commodo eget, egestas vel dui. Donec vulputate nec orci

Cras metus lectus, pellentesque ullamcorper bibendum a, interdum non ligula. In ultrices sodales iaculis. Ut ipsum felis,

eleifend non nunc ut, pharetra molestie ex. In volutpat ante ex. Suspendisse bibendum tortor a lectus consectetur

scelerisque. Ut ut lacus dui. Ut non molestie velit. Sed efficitur enim in venenatis tristique. Mauris pulvinar libero quis

faucibus consectetur.

Sed dignissim placerat enim et aliquet. Aenean consectetur interdum massa at cursus. Maecenas aliquam, tortor a eleifend

aliquam, tellus orci fringilla arcu, id dictum lacus risus id nunc. Curabitur quis dolor a ex cursus iaculis. Nulla bibendum

hendrerit orci, nec aliquam ipsum mollis nec. Vestibulum aliquet, urna nec ullamcorper gravida, tortor est porta leo, ut

aliquet mi enim non turpis. Vestibulum ante ipsum primis in faucibus orci luctus

Journal of Photochemistry & Photobiology, A: Chemistry, 407 (2021) 113033. doi:10.1016/j.jphotochem.2020.113033

Lorem ipsum dolor sit amet, consectetur adipiscing elit. Ut vulputate augue eget odio placerat, in consectetur orci tincidunt.

In hac habitasse platea dictumst. Aliquam efficitur metus ligula, sit amet vehicula ligula rutrum ut. Duis mollis nibh

fringilla lacus maximus, vitae lobortis metus volutpat. Suspendisse ut sapien erat. Pellentesque commodo nulla vitae

facilisis dignissim. Vivamus at orci mi. Donec tristique rhoncus elit ac dapibus.

Pellentesque rhoncus tempor nisl, at porttitor ipsum suscipit quis. Proin mattis, urna id ultricies volutpat, augue dui

scelerisque purus, et tristique libero justo sed quam. Class aptent taciti sociosqu ad litora torquent per conubia nostra, per

inceptos himenaeos. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.

Vestibulum ipsum arcu, cursus nec commodo eget, egestas vel dui. Donec vulputate nec orci

Vestibulum metus tellus, lobortis non dictum ac, dignissim at mauris. Ut ornare, diam quis fermentum finibus, eros lacus

tristique orci, ut molestie lectus justo ut odio. Vivamus egestas enim turpis. Aenean tempor malesuada odio non ornare.

Suspendisse scelerisque leo urna, convallis tristique ligula commodo vel. Quisque lectus augue, interdum at viverra vitae,

bibendum nec leo. Duis id rhoncus felis

Ut id mauris at velit placerat dignissim vel eu tellus. Donec erat ligula, blandit sed mauris in, laoreet lacinia felis. Ut et

risus purus. Praesent eget gravida nunc. Nunc id nisl commodo mauris maximus ultricies. Etiam congue aliquam elit, a

sollicitudin velit tincidunt sed. Integer consequat erat at turpis fringilla elementum. Phasellus scelerisque dui nec molestie

scelerisque. Phasellus ut mattis metus. Duis lectus ipsum,

Lorem ipsum dolor sit amet, consectetur adipiscing elit. Aliquam tempor aliquet risus, nec auctor ante ultrices vel. Nam

rutrum justo quis magna ornare, non lobortis purus faucibus. In hac habitasse platea dictumst. Vivamus imperdiet est vel

massa fringilla fringilla. Curabitur eros nulla, ornare quis sollicitudin ac, accumsan in tellus. Mauris tempus efficitur mi et

scelerisque. Duis diam arcu, facilisis vel eleifend vitae, congue eu nulla

Journal of Photochemistry & Photobiology, A: Chemistry, 407 (2021) 113033. doi:10.1016/j.jphotochem.2020.113033

Etiam dapibus tincidunt pulvinar. Cras lorem felis, mattis sodales congue sed, semper eu lorem. Lorem ipsum dolor sit

amet, consectetur adipiscing elit. Proin faucibus est dictum, pulvinar dui vitae, elementum leo. Maecenas elementum

consequat nisl ut feugiat. Morbi dignissim ex vitae malesuada imperdiet. In blandit, arcu at finibus egestas, neque nisi

egestas diam, et fringilla orci est ut ligula. Pellentesque habitant morbi tristique senectus et

Sed dignissim placerat enim et aliquet. Aenean consectetur interdum massa at cursus. Maecenas aliquam, tortor a eleifend

aliquam, tellus orci fringilla arcu, id dictum lacus risus id nunc. Curabitur quis dolor a ex cursus iaculis. Nulla bibendum

hendrerit orci, nec aliquam ipsum mollis nec. Vestibulum aliquet, urna nec ullamcorper gravida, tortor est porta leo, ut

aliquet mi enim non turpis. Vestibulum ante ipsum primis in faucibus orci luctus

Aliquam faucibus maximus augue vitae molestie. Vivamus a odio ullamcorper, hendrerit nisi a, condimentum lectus.

Phasellus elementum, mauris id consequat fermentum, lorem lectus vehicula elit, in tempor nunc libero et nisl. Interdum et

malesuada fames ac ante ipsum primis in faucibus. Praesent ac nibh libero. Nunc tristique ac erat vitae scelerisque. Donec

ultricies suscipit enim, molestie convallis dui iaculis sed.

Cras metus lectus, pellentesque ullamcorper bibendum a, interdum non ligula. In ultrices sodales iaculis. Ut ipsum felis,

eleifend non nunc ut, pharetra molestie ex. In volutpat ante ex. Suspendisse bibendum tortor a lectus consectetur

scelerisque. Ut ut lacus dui. Ut non molestie velit. Sed efficitur enim in venenatis tristique. Mauris pulvinar libero quis

faucibus consectetur.

Sed ut perspiciatis unde omnis iste natus error sit voluptatem accusantium doloremque laudantium, totam rem aperiam,

eaque ipsa quae ab illo inventore veritatis et quasi architecto beatae vitae dicta sunt explicabo. Nemo enim ipsam

voluptatem quia voluptas sit aspernatur aut odit aut fugit, sed quia consequuntur magni dolores eos qui ratione voluptatem

sequi nesciunt. Neque porro quisquam est, qui dolorem ipsum quia dolor sit amet, consectetur

Journal of Photochemistry & Photobiology, A: Chemistry, 407 (2021) 113033. doi:10.1016/j.jphotochem.2020.113033

Curabitur varius est id magna facilisis, in suscipit tellus auctor. Donec suscipit sed ligula id condimentum. Cras ultrices

nisl non nisl interdum, at tincidunt ante tempor. Sed vitae elit quam. Mauris eget vehicula ligula, id sollicitudin ante.

Nullam semper venenatis sollicitudin. Etiam sem enim, rhoncus at lobortis vel, mattis et mauris. Ut posuere nisi ac lacus

pulvinar mollis.