PHOTOSENSITIZED CYCLOADDITION REACTIONS<sup>1</sup>

Hammond, George S.; Turro, Nicholas J.; Fischer, Alfred

doi:10.1021/ja01483a051

Cited by 190 publications

(93 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Based on an estimate of 300 kJ mol for the lowest triplet state of NBD [7], conventional triplet sensitization might allow use of longer wavelengths. Both organic chromophores [8] and, more recently, Cu(I) complexes [9][10][11][12] have been employed as sensitizers. Even in these systems, however, ultraviolet light is necessary to achieve reaction (4).…”

Section: Photoisomerizationmentioning

confidence: 99%

“…M+X-YX--W-Y (8) The oxidation state of the metal atom is formally increased by two on the addition of XY. These reactions are best known for square planar complexes M. Where XY is a halogen the concept is intuitively appealing; but where the process involves an alkyl halide or a protic acid (e. g., HC1, CH3NO2, or PhCECH) the term oxidation seems less appropriate.…”

Section: Photoionizationmentioning

confidence: 99%

“…Solutions of Mo2X (X=Cl,Br) underwent oxidative addition of HX from aqueous solution when exposed to 254 run light [27]. The Mo2X H3 [not an oxidative-addition product in the sense of reaction (8), but at least one in wich H+ has formally been reduced and Mo(II) oxidized] then decomposed, giving H2 and a dinuclear Mo(III) species.…”

Section: Photoionizationmentioning

confidence: 99%

See 2 more Smart Citations

Solar energy storage reactions involving metal complexes

Maverick¹,

Gray²

1980

Pure and Applied Chemistry

View full text Add to dashboard Cite

-Photochemical properties of transition metal complexes are discussed as they relate to possible schemes for energy storage. Complexes of copper(I) with r-acceptor ligamds have been used to sensitize isomerizations of organic molecules, and there is room for considerable further investigation in this area. Electron transfer reactions have been more intensively studied. These reactions fall into three broad categories: ionization, oxidative addition/reductive elimination, and excited state electron transfer. Experiments in the first two categories have ierally led to rather poor storage efficiency and have required ultraviolet light. But long-lived excited states of coordination compounds can participate in chemical reactions with high efficiency, and such systems are promising for solar energy storage. Specific systems of this type that are discussed in detail involve electron transfer quenching of the lowest emissive excited states of Ru(2,2'_bipyridine), M (diisocyanoalkane) (M=Rh,Ir), and Mo6Cl.

show abstract

Section: Photoisomerizationmentioning

confidence: 99%

Section: Photoionizationmentioning

confidence: 99%

See 1 more Smart Citation

Solar energy storage reactions involving metal complexes

Maverick¹,

Gray²

1980

Pure and Applied Chemistry

View full text Add to dashboard Cite

show abstract

“…Non-catalyzed isomerization of Q proceeds only slowly at high temperature (t 1/2 >14h, 140 o C) [5], since 2σ-2π ring opening process leading to N is forbidden by Woodward-Hoffmann rules [6]. Chemical behavior and reactivity of quadricyclane (Q ) is governed by several factors, including high strain energy, surprisingly low first ionization potential (IP; adiabatic -7.40 eV, vertical -8.3 [7], 8.43 [8], 8.45 [9] eV) and one of the lowest oxidation potential known for strained polycyclic molecules [ E 1/2 =0.91 V (SCE), vs. 1.56 V for N , 1.95 V for norbornene or 2.12 V for nortricyclane] [10].…”

mentioning

confidence: 99%

Synthetic Chemistry of Quadricyclane

Петров¹,

Vasil'ev²

2006

COS

View full text Add to dashboard Cite

“…The photochemical valence isomerization between norbornadiene (NBD) and quadricyclane (QC) is of great interest as a solar energy conversion and storage system, [1][2][3][4] because NBD can convert solar energy into 96 kJ/mol of thermal energy through the strain in QC.…”

mentioning

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

View full text Add to dashboard Cite

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...

show abstract

PHOTOSENSITIZED CYCLOADDITION REACTIONS¹

Cited by 190 publications

References 0 publications

Solar energy storage reactions involving metal complexes

Solar energy storage reactions involving metal complexes

Synthetic Chemistry of Quadricyclane

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

Contact Info

Product

Resources

About

PHOTOSENSITIZED CYCLOADDITION REACTIONS1

Cited by 190 publications

References 0 publications

Solar energy storage reactions involving metal complexes

Solar energy storage reactions involving metal complexes

Synthetic Chemistry of Quadricyclane

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

Contact Info

Product

Resources

About

PHOTOSENSITIZED CYCLOADDITION REACTIONS¹