Two‐Component Liquid Crystals as Chiral Reaction Media: Highly Enantioselective Photodimerization of an Anthracene Derivative Driven by the Ordered Microenvironment

Ishida, Yasuhiro; Kai, Yukiko; Kato, S.; Misawa, Aya; Amano, Sayaka; Matsuoka, Yuki; Saigo, Kazuhiko

doi:10.1002/anie.200803242

Cited by 81 publications

(52 citation statements)

References 52 publications

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“…20 It is also considered that the dimers D-2COOH form hydrogen bonding with two carboxylic acid groups of the neighboring photodimers, which promote segregation of the crystals in IL. It is to note that the photodifferentiation phenomenon found in this study has not been reported for the previous [4+4] cycloaddition reaction of anthracene carboxylic acids in organogels, 12,21 liquid crystals, 22,23 and ionic liquids, 24,25 probably due to the presence of organic solvents or the use of 2-anthracenecarboxylate, whose pK a is less influenced by photodimerization.…”

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confidence: 62%

Photoinduced Crystallization in Ionic Liquids: Photodimerization-induced Equilibrium Shift and Crystal Patterning

Hisamitsu

Yanai²,

Fujikawa³

et al. 2015

Chemistry Letters

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An ionic liquid (IL) composed of 9-anthracenecarboxylate anion and ammonium cation possessing three diethylene glycol chains shows phototriggered dimerization of anthracence chromophores. It causes segregation and crystallization of protonated 9-anthracenecarboxylic acid dimer, which is associated with the concurrent liberation of the free amine in the IL. This work provides a new molecular design for photoresponsive ILs, whose first application for site-selective photopatterning is demonstrated.Ionic liquids (ILs) have attracted considerable interest from many researchers because of their unique physical and chemical properties, which are tunable depending on their constituents. 13One of the evolving areas in this field is the introduction of mesoscopic interfaces 4,5 for developing novel interfacial phenomena. 6,7 In this regard, ILs containing π-conjugated chromophores are attractive as photofunctional soft materials that show new applications such as condensed luminescent materials 810 and solar thermal storage. 11 We have recently reported the photoliquefaction of ionic crystals to ILs by employing cationic azobenzene derivatives covalently modified with three flexible diethylene glycol chains in the ammonium head group. 11 Photon energy was effectively stored not only as the conformational energy of the azobenzene unit but also as the latent heat of crystallization, where the integration of self-assembly phenomena and photoresponsive ILs opened the doors to the phase crossover chemistry. 11Here, we describe a new photoresponsive IL that shows photoinduced crystallization phenomena. It is formed from a well-known Brønsted acid (9-anthracenecarboxylic acid, A-COOH) 12,13 and a Brønsted base having three flexible diethylene glycol chains (tris[2(2methoxyethoxy)ethyl]amine, 1). This integration based on acidbase neutralization gives a chromophoric IL [1-H] +

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contrasting

confidence: 62%

Photoinduced Crystallization in Ionic Liquids: Photodimerization-induced Equilibrium Shift and Crystal Patterning

Hisamitsu

Yanai²,

Fujikawa³

et al. 2015

Chemistry Letters

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“…3 Such an orientation can be controlled using directional supermolecular interactions such as hydrogen bonding and π-π stacking. 4 To induce the reversible crystalline phase reaction, we focused on the hexanuclear cluster [ 3 ] -anion. Each Fe II is further coordinated with one acetonitrile and two water molecules.…”

mentioning

confidence: 99%

Reversible Single-Crystal-to-Single-Crystal Transformation from Achiral Antiferromagnetic Hexanuclears to a Chiral Ferrimagnetic Double Zigzag Chain

et al. 2009

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“…43,44 The [4+4] photodimerization of 2 -anthracenecarboxylate (AC) accommodated in γ -CD and its derivatives was investigated in detail. 45 Inoue and co -workers have recently reinvestigated the photodimerization of AC from the chiral point of view by using a variety of chiral hosts. γ -CD forms very stable 1 : 2 host -guest complex with AC in aqueous buffer solution with association constants of K 1 = 160 M − 1 and K 2 = 38500 M − 1 .…”

Section: Unimolecular Reactionsmentioning

confidence: 99%

Reaction Control by Molecular Recognition – A Survey from the Photochemical Perspective

Yang

Liu

et al. 2010

Molecular Encapsulation

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Molecular recognition through non -covalent interactions between two or more molecules has attracted much attention from a broad spectrum of chemists for a long period of time and has already found many applications in various areas of science and technology. The concept of molecular recognition was fi rst developed for biomolecular systems such as enzyme, antibody and DNA, which can selectively bind the specifi c target molecules through non -covalent weak interactions, including hydrogen bonding, van der Waals, dipole -dipole, charge -dipole and hydrophobic interactions. 1 -3 Recent studies on artifi cial host -guest systems have revealed that molecular recognition is the essential conceptual basis for supramolecular chemistry and nanotechnology. 4,5 Reaction control through complexation of substrate by supramolecular host is a relatively new idea compared to the conventional approaches that involve simple collisional attack or coordination of substrate to metal. Multiple non -covalent interactions in supramolecular assembly bind and locate a site -specifi c substrate in the right position, orientation and conformation near the catalyst or active site, stabilize the high -energy transition state, and eventually make the reaction faster and more selective. Typical examples are found in enzymatic reactions, which proceed with high specifi city and effi ciency in aqueous solutions under mild conditions. These observations in natural systems have inspired Molecular Encapsulation: Organic Reactions in Constrained SystemsEdited by Udo H. Brinker and Jean-Luc Mieusset

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Two‐Component Liquid Crystals as Chiral Reaction Media: Highly Enantioselective Photodimerization of an Anthracene Derivative Driven by the Ordered Microenvironment

Abstract: Tailored to the reaction: Within a liquid‐crystalline matrix provided by a chiral amphiphilic amino alcohol, the photodimerization of an anthracenecarboxylic acid proceeds with high probability and with excellent regio‐, diastereo‐, and enantioselectivities (up to 81 % ee).

Cited by 81 publications

References 52 publications

Photoinduced Crystallization in Ionic Liquids: Photodimerization-induced Equilibrium Shift and Crystal Patterning

Photoinduced Crystallization in Ionic Liquids: Photodimerization-induced Equilibrium Shift and Crystal Patterning

Reversible Single-Crystal-to-Single-Crystal Transformation from Achiral Antiferromagnetic Hexanuclears to a Chiral Ferrimagnetic Double Zigzag Chain

Reaction Control by Molecular Recognition – A Survey from the Photochemical Perspective

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