Synthesis of New Photoresponsive Polyesters Containing Donor−Acceptor Norbornadiene (D−A NBD) Residues by the Polyaddition of D−A NBD Dicarboxylic Acids with Bis(epoxide)s and Their Photochemical Properties

Ikeda, Akihiko; Kameyama, and Atsushi; Nishikubo, Tadatomi; Nagai, Takabumi

doi:10.1021/ma0015830

Cited by 19 publications

(29 citation statements)

References 16 publications

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“…As shown in Figure 4 for polymer P1b, the absorption maximum at 278 nm decreases gradually on irradiation indicating a good conversion of the NBD into QC after 20 min. In addition, and as it is reported in the literature,19, 21, 31, 32 an isosbestic point at 228 nm was observed. This phenomenon, which was observed for all the samples means that the photochemical valence isomerization of the NBD units of polymer chains to the corresponding QC groups occurred selectively without side reactions.…”

Section: Resultssupporting

confidence: 86%

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Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

Oueslati

Romdhane

Martin

et al. 2011

J. Polym. Sci. A Polym. Chem.

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A novel pentamethylated norbornadiene (NBD) based dianhydride, α,α′‐bis‐(3,4,5,6,7‐pentamethylcyclopenta‐2,4‐dienyl)meta‐xylene‐1,2‐dianhydride (3), was prepared from α,α′‐bis‐(pentamethylcyclopentadienyl)meta‐xylene (1) and acetylene dicarboxylic acid. The bis‐adduct formed via Diels–Alder reaction afforded tetra‐acid (2), which was chemically cyclodehydrated to lead the targeted dianhydride (3). New polyimides containing NBD moieties in the main chain were prepared from the dianhydride monomer (3) and various aromatic diamines. The chemical structure of the polymers was confirmed by both 1H and 13C NMR analysis. Their Molecular weights were also measured by SEC. All of these polyimides are soluble at room temperature in common organic solvents, such as chloroform, dichloromethane, THF, DMSO, DMF, and NMP, and show good thermal stabilities. The photochemical isomerization of the NBD into quadricyclane (QC) was investigated by UV/vis spectrophotometry from polymer films using visible sunlight as irradiation source. It was found that the kinetic rate of the conversion NBD‐QC which proceeded smoothly is a first kinetic order. The stored energies released by the transformation of QC groups into NBD ones of the irradiated polymer films were also evaluated by DSC measurement and were found to be around 90 kJ mol−1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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Section: Resultssupporting

confidence: 86%

“…Because the experiences were performed with very thin polymer films, it was assumed that the Beer Lambert's law was applicable. So, in this study, this relation was used according to the work published in the literature 18, 20, 31, 33…”

Section: Resultsmentioning

confidence: 99%

Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

Oueslati

Romdhane

Martin

et al. 2011

J. Polym. Sci. A Polym. Chem.

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“…Molecular Solar Thermal (MOST) technology utilises energy from the sun to convert photoswitchable molecules into a higher energy structure, with the energy able to be stored for prolonged periods . MOST has been represented by several organic based T‐type photochromic molecular motifs such as azobenzene 1 , dihydroazulene 2 , tetracarbonyl‐dirutheniumdifulvalene 3 , and the norbornadiene‐quadricyclane couple ( NBD4‐QC4 ) (Figure ) . T‐type photoswitches are interconvertible between two states, where a light‐driven reaction forms a metastable photo‐isomer that can be thermally returned to the photoactive parent molecule .…”

Section: Introductionmentioning

confidence: 99%

Tuning Molecular Solar Thermal Properties by Modification of a Promising Norbornadiene Photoswitch

et al. 2019

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Carefully targeted modifications to the norbornadiene‐quadricyclane couple should give molecules with great potential for solar energy storage. Here we report the synthesis of derivatives of a well‐studied compound, 2‐cyano‐3‐anisyl norbornadiene (NBD5). The conjugation was extended by conversion of the nitrile into acrylonitrile and acrylate derivatives over two steps. Despite red‐shifting the absorbance properties, the metastable quadricyclanes exhibited extremely short lifetimes. Meanwhile, treatment of NBD5 with acetyl halides in the presence of aluminum trihalides led to the formation of 7‐acetyl norbornenes through a Wagner–Meerwein rearrangement. Subsequent transformations made it possible to synthesise norbornadienes with varying degrees of steric bulk at the 7‐position of the molecular scaffold. It was found that the bulkier this group was, the more stable the quadricyclane form. This reaction sequence allows for the synthesis of norbornadiene derivatives which are more suited to molecular solar thermal applications in domestic heating despite providing a slightly lower energy density.

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“…21,22 Furthermore, Nishikubo et al [23][24][25][26] synthesized the polymers containing D-A NBD moieties in the main chain or side chain and examined their photo-chemical valence isomerization. It was found that their synthesized polymers had high photochemical reactivities and good fatigues of resistance.…”

Section: Introductionmentioning

confidence: 99%

“…It was found that their synthesized polymers had high photochemical reactivities and good fatigues of resistance. [23][24][25][26] Furthermore, it is expected that the thermal storage energies of the polymers increase with increasing the ratio of the NBD moieties.From these backgrounds, in this article, we examined the synthesis of the polymers containing D-A NBD moieties in the both main and side chains. The polyesters with D-A moieties in the main chain were obtained by the polyaddition of the bisepoxides with NBD groups and carboxylic dichlorides.…”

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confidence: 99%

Synthesis and Photochemical Reaction of Poly(ester)s Containing Donor–Acceptor Type Norbornadiene Residues in the Both Main and Side Chains

Ono

Kawashima

Kudo

et al. 2005

Polym J

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ABSTRACT:The synthesis and photochemical valence isomerization of polymers containing donor-acceptor type norbornadiene (D-A NBD) residues in both main and side chains, by the polyaddition of 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-2,5-norbornadiene-2,3-dicarboxylic acid diglycidyl ester (D-A NDGE) with terephthaloyl chloride follows by substitution reactions of the resulting polymer with potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-methylester-2,5-NBD-2-carboxylate, potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-(N,N-dipropylcarbamoyl)-2,5-NBD-2-carboxylate, and potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-(N-methyl-Nphenylcarbamoyl)-2,5-NBD-2-carboxylate, respectively. The photochemical valence isomerization of the synthesized poly(ester)s (P-1-P-4, and P-5a-c) was examined in tetrahydrofuran solution or in the film state upon irradiation with a 500-W xenon lamp, and it was found that each photochemical reaction proceeded very smoothly. It was also observed that the rate of the photochemical reaction of the NBD polymers increased efficiently by the addition of 4,4 0 -bis-(diethylamino)benzophenone (BEBP) as a photo-sensitizer in the film state. The stored thermal energies of the irradiated polymers were evaluated by DSC analysis to be 75-153 J/g. [DOI 10.1295/polymj.37.246] KEY WORDS Donor-Acceptor Type Norbornadiene / Polyaddition / Photochemical Valence Isomerization / Photo-sensitizer / Stored Thermal Energy / The photochemical valence isomerization between norbornadiene (NBD) and quadricyclane (QC) is of great interest as a solar energy conversion and storage system, 1-4 because NBD can convert solar energy into 96 kJ/mol of thermal energy through the strain in QC.Nishikubo et al. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] reported the synthesis of photoreactive polymers containing NBD residues in the main chain or the side chain, and it was observed that the NBD residues in the polymers converted smoothly to form QC ones. These NBD-containing polymers had high stored thermal energies. However, these synthesized polymers were not suitable to applications as a material for solar energy conversion and storage systems, because they did not have strong absorption band into visible region and did not have good durabilities in the reversible photochemical reaction.On the other hand, it is known that donor-acceptor type norbornadiene (D-A NBD) derivatives had absorption band into visible region and converted to the corresponding QC derivatives in high quantum yield. 21,22 Furthermore, Nishikubo et al. [23][24][25][26] synthesized the polymers containing D-A NBD moieties in the main chain or side chain and examined their photo-chemical valence isomerization. It was found that their synthesized polymers had high photochemical reactivities and good fatigues of resistance. [23][24][25][26] Furthermore, it is expected that the thermal storage energies of the polymers increase with increasing the ratio of the NBD moieties.From these backgrounds, in this article, we examined...

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Synthesis of New Photoresponsive Polyesters Containing Donor−Acceptor Norbornadiene (D−A NBD) Residues by the Polyaddition of D−A NBD Dicarboxylic Acids with Bis(epoxide)s and Their Photochemical Properties

Cited by 19 publications

References 16 publications

Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

Tuning Molecular Solar Thermal Properties by Modification of a Promising Norbornadiene Photoswitch

Synthesis and Photochemical Reaction of Poly(ester)s Containing Donor–Acceptor Type Norbornadiene Residues in the Both Main and Side Chains

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