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The structural and electronic properties of 3,3′-azothiophene photo-switching systems

Published on Jan 1, 2019in Physical Chemistry Chemical Physics3.57
· DOI :10.1039/c8cp06059b
Patrick R. Huddleston6
Estimated H-index: 6
(NTU: Nottingham Trent University),
Victor Volkov8
Estimated H-index: 8
(NTU: Nottingham Trent University),
Carole C. Perry44
Estimated H-index: 44
(NTU: Nottingham Trent University)
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Abstract
Diversity of photo-switching structural elements open up new opportunities in the engineering of light driven reshaping of matter, in catalysis on-click including photodynamic cancer therapy, in light sensitive transport control and in data storage. Assisted with quantum calculations we explore the photo-physical properties of novel 3,3-azothiophene molecular systems, the synthesis of which we reported recently. In the considered azothiophenes, upon exposure to radiation at 365 nm and at 530 nm, we observed effective anti(trans) to syn(cis) and syn(cis) to anti(trans) isomerization of the -N=N- moiety, respectively. In contrast to azobenzene based photo-switchable molecular systems, the syn(cis) to anti(trans) isomerization in the azothiophenes studied, does not take place at 22 oC in the dark. Temperature dependent experiments and theoretical studies suggest a slightly higher barrier for such processes than for azobenzene which we attribute to specific structural and electronic properties of the thiophene ring and the nature of the side groups. We discuss the potential of the observed properties in the development of novel molecular photo-switching machinery to promote biocatalytic applications at interfaces.
  • References (47)
  • Citations (1)
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References47
Newest
Published on Feb 21, 2018in Journal of Chemical Theory and Computation5.31
Anja Muždalo1
Estimated H-index: 1
(MPG: Max Planck Society),
Peter Saalfrank1
Estimated H-index: 1
+ 1 AuthorsMark Santer7
Estimated H-index: 7
(MPG: Max Planck Society)
Azobenzene-based molecular photoswitches are becoming increasingly important for the development of photoresponsive, functional soft-matter material systems. Upon illumination with light, fast interconversion between a more stable trans and a metastable cis configuration can be established resulting in pronounced changes in conformation, dipole moment or hydrophobicity. A rational design of functional photosensitive molecules with embedded azo moieties requires a thorough understanding of isomer...
Published on Jan 1, 2018in Organic Electronics3.50
Ting-Ting Yin3
Estimated H-index: 3
(JLU: Jilin University),
Zeng-Xia Zhao3
Estimated H-index: 3
(JLU: Jilin University),
Hong-Xing Zhang26
Estimated H-index: 26
(JLU: Jilin University)
Abstract Besides the photochromism isomerization, scientists are likely to focus more and more on the influence on the electrochemical reduction conditions of the azobenzene isomerization process. Diverse azobenzene compounds were chosen to study the behavior of their trans and cis isomers upon electrochemical reduction. Hence, thermal reaction mechanisms for the neutral, cationic and anionic azobenzene derivatives isomerization with a wide variety of electron-donating and electron-withdrawing g...
Published on Jan 1, 2018in Physical Chemistry Chemical Physics3.57
Andrzej Miniewicz24
Estimated H-index: 24
,
Hanna Orlikowska2
Estimated H-index: 2
+ 1 AuthorsStanislaw Bartkiewicz19
Estimated H-index: 19
Single-component azobenzene-based phototropic liquid crystals (PtLC) are promising materials that have started to be explored for photonic applications. One of the essential factors determining the applicability of these materials is the rate of the thermally driven cis–trans isomerization. In this paper, the kinetics of the thermal back cis-to-trans reaction in a pure 4-hexyl-4′-methoxyazobenzene (6-AB-O1) compound in its isotropic liquid and nematic phases is studied (the undoped LC). The reac...
Published on Jul 29, 2017in Molecules3.06
Guido Angelini14
Estimated H-index: 14
,
Cristina Campestre13
Estimated H-index: 13
+ 1 AuthorsCarla Gasbarri12
Estimated H-index: 12
BMIM PF6 (1-butyl-3-methylimidazolium hexafluorophosphate) and BMIM Tf2N (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) are two conventional room-temperature ionic liquids widely employed and investigated as reaction media. Despite the presence of the same imidazolium ring in their structure they are different in many chemical and physical properties due to the nature of the anions. The thermal cis-trans isomerization of an electronically activated azobenzene have been used as r...
Published on Feb 1, 2016in Dyes and Pigments4.02
Ning Zhu1
Estimated H-index: 1
(ECUST: East China University of Science and Technology),
Xin Li38
Estimated H-index: 38
(KTH: Royal Institute of Technology)
+ 1 AuthorsXiang Ma30
Estimated H-index: 30
(ECUST: East China University of Science and Technology)
Abstract Two novel photo-responsive chiral cyclic molecular switches constituted of stiff stilbene and binaphthyl moieties connected through alkyl chains of different length were fabricated. The cyclization synthetic strategy employed herein made it convenient to obtain the pure Z isomers rather than Z/E isomer mixtures. The detailed photo-switching behaviors of target compounds were studied by the UV–Vis absorption and circular dichroism spectra in dichloromethane. The twist angles of the binap...
Published on Jan 13, 2016in ACS Applied Materials & Interfaces8.46
J. Pablo Palafox-Hernandez7
Estimated H-index: 7
(Deakin University),
Chang-Keun Lim11
Estimated H-index: 11
(UB: University at Buffalo)
+ 7 AuthorsTiffany R. Walsh30
Estimated H-index: 30
(Deakin University)
Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered c...
Published on Jan 1, 2016in Organic and Biomolecular Chemistry3.49
Jonathon E. Sheldon2
Estimated H-index: 2
(VCU: Virginia Commonwealth University),
M. Michael Dcona4
Estimated H-index: 4
(VCU: Virginia Commonwealth University)
+ 2 AuthorsMatthew C. T. Hartman12
Estimated H-index: 12
(VCU: Virginia Commonwealth University)
Combretastatin A-4 (CA4) is highly potent anticancer drug that acts as an inhibitor of tubulin polymerization. The core of the CA4 structure contains a cis-stilbene, and it is known that the trans isomer is significantly less potent. We prepared an azobenzene analog of CA4 (Azo-CA4) that shows 13–35 fold enhancement in potency upon illumination. EC50 values in the light were in the mid nM range. Due to its ability to thermally revert to less toxic trans form, Azo-CA4 also has the ability to auto...
Published in Tetrahedron Letters2.26
Sandra Wiedbrauk7
Estimated H-index: 7
(LMU: Ludwig Maximilian University of Munich),
Henry Dube15
Estimated H-index: 15
(LMU: Ludwig Maximilian University of Munich)
Abstract Hemithioindigo (HTI) is an emerging photoswitch with many advantageous properties compared to the commonly used photoswitches like azobenzenes, spiropyranes, or dithienylethenes. In this DIGEST the syntheses, physical and photophysical properties of HTI photoswitches and mechanistic explanations for the latter are reviewed. Emphasis will be placed on those distinct properties that render HTIs into unique phototools. Additionally, a broad variety of applications ranging from supramolecul...
Published on Mar 24, 2014in Angewandte Chemie12.26
Oleg Babii6
Estimated H-index: 6
(KIT: Karlsruhe Institute of Technology),
Sergii Afonin25
Estimated H-index: 25
+ 6 AuthorsIgor V. Komarov23
Estimated H-index: 23
(KNU: Taras Shevchenko National University of Kyiv)
Photobiological processes in nature are usually triggered by nonpeptidic chromophores or by modified side chains. A system is presented in which the polypeptide backbone itself can be conformationally switched by light. An amino acid analogue was designed and synthesized based on a reversibly photoisomerizable diarylethene scaffold. This analogue was incorporated into the cyclic backbone of the antimicrobial peptide gramicidin S at several sites. The biological activity of the resulting peptidom...
Published on Jan 1, 2014in Materials horizons14.36
Rahul Dev Mukhopadhyay7
Estimated H-index: 7
(National Institute for Interdisciplinary Science and Technology),
Vakayil K. Praveen24
Estimated H-index: 24
(National Institute for Interdisciplinary Science and Technology),
Ayyappanpillai Ajayaghosh53
Estimated H-index: 53
(National Institute for Interdisciplinary Science and Technology)
Photoinduced cis–trans isomerisation of azobenzene has been an inspiration to chemists to design smart materials that respond to light. Lately, this chemistry has also made a mark in the emerging area of metal–organic materials. If one can regulate the properties of porous hybrid materials with light, their scope of applications can be expanded. The field is shown to be promising and gradually progressing from nano to mesospace. However, one needs more in-depth research to deliver materials that...
Cited By1
Newest
Published on Aug 1, 2019in Polymer3.77
Lanbo Shen (SDU: Shandong University), Xirong Huang (SDU: Shandong University)
Abstract In this work, the azobenzene group-containing carboxylic acid salt azobenzene-4,4′-dicarboxylate disodium salt (ADDS) was selected as the dopant for the controlled synthesis of nanostructured polypyrrole (PPy). By controlling the cis - trans configuration of ADDS (via ultraviolet light irradiation) as well as the concentration of divalent ADDS anion (via the medium pH alteration), a series of ADDS-doped PPy hydrogels with different morphologies and electrical properties were prepared ac...