Photoswitching of Dihydroazulene Derivatives in Liquid-Crystalline Host Systems
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Photoswitching of Dihydroazulene Derivatives in Liquid-Crystalline Host Systems. / Petersen, Anne Ugleholdt; Jevric, Martyn; Mandle, Richard J.; Sims, Mark T.; Moore, John N.; Cowling, Stephen J.; Goodby, John W.; Nielsen, Mogens Brøndsted.
I: Chemistry: A European Journal, Bind 23, Nr. 21, 2017, s. 5090-5103.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Photoswitching of Dihydroazulene Derivatives in Liquid-Crystalline Host Systems
AU - Petersen, Anne Ugleholdt
AU - Jevric, Martyn
AU - Mandle, Richard J.
AU - Sims, Mark T.
AU - Moore, John N.
AU - Cowling, Stephen J.
AU - Goodby, John W.
AU - Nielsen, Mogens Brøndsted
PY - 2017
Y1 - 2017
N2 - Photoswitches and dyes in the liquid-crystalline nematic phase have the potential for use in a wide range of applications. A large order parameter is desirable to maximize the change in properties induced by an external stimulus. A set of photochromic and nonphotochromic dyes were investigated for these applications. It was found that a bent-shaped 7-substituted dihydroazulene (DHA) photoswitch exhibited liquid-crystalline properties. Further investigation demonstrated that this material actually followed two distinct reaction pathways on heating, to a deactivated form by a 1,5-sigmatropic shift and to a linear 6-substituted DHA. In addition, elimination of hydrogen cyanide from the photoactive DHA gave both bent and linear azulene dyes. In a nematic host that has no absorbance around 350nm, it was found that only the linear DHA derivative has nematic properties; however, both 6- and 7-substituted DHAs were found to have large order parameters. In the nematic host, ring opening of either DHA to the corresponding vinylheptafulvene resulted in a decrease in dichroic order parameter and an unusually fast back-reaction to a mixture of both DHAs. Likewise, only the linear azulene derivative showed mesomorphic properties. In the same nematic host, large order parameters were also observed for these dyes.
AB - Photoswitches and dyes in the liquid-crystalline nematic phase have the potential for use in a wide range of applications. A large order parameter is desirable to maximize the change in properties induced by an external stimulus. A set of photochromic and nonphotochromic dyes were investigated for these applications. It was found that a bent-shaped 7-substituted dihydroazulene (DHA) photoswitch exhibited liquid-crystalline properties. Further investigation demonstrated that this material actually followed two distinct reaction pathways on heating, to a deactivated form by a 1,5-sigmatropic shift and to a linear 6-substituted DHA. In addition, elimination of hydrogen cyanide from the photoactive DHA gave both bent and linear azulene dyes. In a nematic host that has no absorbance around 350nm, it was found that only the linear DHA derivative has nematic properties; however, both 6- and 7-substituted DHAs were found to have large order parameters. In the nematic host, ring opening of either DHA to the corresponding vinylheptafulvene resulted in a decrease in dichroic order parameter and an unusually fast back-reaction to a mixture of both DHAs. Likewise, only the linear azulene derivative showed mesomorphic properties. In the same nematic host, large order parameters were also observed for these dyes.
KW - Dyes/pigments
KW - Electrocyclic reactions
KW - Fused-ring systems
KW - Host-guest systems
KW - Liquid crystals
U2 - 10.1002/chem.201700055
DO - 10.1002/chem.201700055
M3 - Journal article
C2 - 28195368
AN - SCOPUS:85016396875
VL - 23
SP - 5090
EP - 5103
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
SN - 0947-6539
IS - 21
ER -
ID: 176610813