Surface photochemistry: semiconductor photoinduced valence isomerization of quadricyclane to norbornadiene

Draper, Anthony M.; Mayo, P. De

doi:10.1016/s0040-4039(00)85421-0

Cited by 14 publications

(6 citation statements)

References 23 publications

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“…There appears to be no correlation between surface area and reactivity except possibly within the same structure type. The most efficient 3~s noted, this transformation was reported in a preliminary form (23). Subsequently and independently, Ikezawa and Kutal confirmed our observations (35 samples are those in the P (cubic) form, the slowest being in the a (hexagonal) form.…”

Section: Resultssupporting

confidence: 76%

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Surface photochemistry: Semiconductor mediated reactions of some saturated strained hydrocarbons

Baird¹,

Draper²,

Mayo³

1988

Can. J. Chem.

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Quadricyclane (1) and 1,8-bishomocubane (2) have been found to undergo valence isomerization to norbornadiene and tricycl0[4.2.2.0~.~]deca-3,7-diene, respectively, on illuminated CdS and ZnO. An electron transfer mechanism is proposed.Quantum yield, solvent effects, the role of oxygen, and the quenching of the reaction were investigated, and were consistent with this interpretation. The thermal reaction of 1 on CdS was also suggested to be an electron transfer process involving, in this case, defects or trapped holes on the surface of the semiconductor. An examination of a series of strained hydrocarbons structurally related to 1 (

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Section: Resultssupporting

confidence: 76%

“…Unanticipated results for the reactivity of 3+-5+ led us to investigate these reactions further by calculations using MM2 and MNDO. A brief report of the conversion of 1 + 2 has been made (23).…”

Section: Introductionmentioning

confidence: 99%

Surface photochemistry: Semiconductor mediated reactions of some saturated strained hydrocarbons

Baird¹,

Draper²,

Mayo³

1988

Can. J. Chem.

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“…Triplet sensitization is not a feasible option as the QC's triplet energy although lower is known to predominantly return to the QC in the ground state without crossing to the NBD surface (12). The lower oxidation potential of QC (QC ~0.91 V; NBD ~1.56 V, SCE) on the other hand is known to favor electron transfer sensitized retro-cycloaddition to regenerate NBD (19,40,42,43,47). MB (reduction potential: À0.47 V, SCE; absorption maximum; 664 nm; E T : 1.5 eV) was used as the electron transfer sensitizer in this study to establish occurrence of this process (73).…”

Section: Resultsmentioning

confidence: 99%

“…Although QC has lower triplet energy than NBD, on the triplet surface, apparently it returns to its ground state via a nearby conical intersection and does not cross over to NBD (12). While in the context of solar energy applications the preferred mode of energy release is by thermally activated catalytic cycles (1,2), we were attracted to the possibility of doing so via the electron transfer sensitization pathway using semiconductors (TiO 2 and CdS) and conventional organic and inorganic sensitizers (19,38,47). Thus, in principle, QC could be prepared from NBD by classic triplet energy transfer sensitization, and the reverse process (energy release) can be realized via well‐investigated electron transfer sensitization.…”

Section: Introductionmentioning

confidence: 99%

Reversible Photoisomerization of Norbornadiene‐Quadricyclane within a Confined Capsule^†

Pradeep

Varadharajan

Ramamurthy

2022

Photochem & Photobiology

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With the desire to develop a sustainable green method to store and release solar energy via a chemical reaction, we have examined the well-investigated norbornadienequadricyclane (NBD-QC) system in water. In this context, we have employed octa acid (OA) as the host that forms a capsule in water. According to 1 H NMR spectra and diffusion constants, OA forms a stable 2:2 complex with both NBD and QC and 1:1:2 mixed complex in the presence of equal amounts of both NBD and QC. The photoconversion of NBD to QC within the OA capsule is clean without side reactions. In this case, OA itself acts as a triplet sensitizer. Recognizing the disadvantage of this supramolecular approach, in the future we plan to look for visible light absorbing sensitizers to perform this conversion. The reverse reaction (QC to NBD) is achieved via electron transfer process with methylene blue as the sensitizer. This reverse reaction is also clean, and no side products were detected. The preliminary results reported here provide "proof of principle" for combining green, sustainable and supramolecular chemistries in the context of solar energy capture and release.

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“…Whereas ZnO did not show any side reaction, such as the formation of NBD dimers, ZnS and CdS produced a small amount of sulfur because of photocorrosion. Interestingly, all catalysts catalyzed the photoisomerization reaction only in the presence of oxygen, which means oxygen played an important role in the photocatalytic process [30]. Photogenerated electrons produced in the semiconductor's conduction band may convert oxygen into a superoxide radical anion, and the positive photogenerated hole produced may draw electrons from NBD, thereby forming the dirradicaloid of NBD.…”

Section: Synthesis With Metal Sulfide Catalystsmentioning

confidence: 99%

Photocatalytic Synthesis of High-Energy-Density Fuel: Catalysts, Mechanisms, and Challenges

Xiao

Zhang

Pan

et al. 2021

Trans. Tianjin Univ.

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High-energy-density liquid hydrocarbon fuels are generally synthesized using various chemical reactions to improve the performance (e.g., range, load, speed) of aerospace vehicles. Compared with conventional fuels, such as aviation kerosene and rocket kerosene, these liquid hydrocarbon fuels possess the advantages of high-energy-density and high volumetric calorific value; therefore, the fuels have important application value. The photocatalytic process has shown great potential for the synthesis of a diverse range of fuels on account of its unique properties, which include good efficiency, clean atomic economy, and low energy consumption. These characteristics have led to the emergence of the photocatalytic process as a promising complement and alternative to traditional thermocatalytic reactions for fuel synthesis. Extensive effort has been made toward the construction of catalysts for the multiple photocatalytic syntheses of high-energy-density fuels. In this review, we aim to summarize the research progress on the photocatalytic synthesis of high-energy-density fuel by using homogeneous and heterogeneous catalytic reactions. Specifically, the synthesis routes, catalysts, mechanistic features, and future challenges for the photocatalytic synthesis of high-energy-density fuel are described in detail. The highlights of this review not only promote the development of the photocatalytic synthesis of high-energy-density fuel but also expand the applications of photocatalysis to other fields. Graphic abstract

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Surface photochemistry: semiconductor photoinduced valence isomerization of quadricyclane to norbornadiene

Cited by 14 publications

References 23 publications

Surface photochemistry: Semiconductor mediated reactions of some saturated strained hydrocarbons

Surface photochemistry: Semiconductor mediated reactions of some saturated strained hydrocarbons

Reversible Photoisomerization of Norbornadiene‐Quadricyclane within a Confined Capsule^†

Photocatalytic Synthesis of High-Energy-Density Fuel: Catalysts, Mechanisms, and Challenges

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Surface photochemistry: semiconductor photoinduced valence isomerization of quadricyclane to norbornadiene

Cited by 14 publications

References 23 publications

Surface photochemistry: Semiconductor mediated reactions of some saturated strained hydrocarbons

Surface photochemistry: Semiconductor mediated reactions of some saturated strained hydrocarbons

Reversible Photoisomerization of Norbornadiene‐Quadricyclane within a Confined Capsule†

Photocatalytic Synthesis of High-Energy-Density Fuel: Catalysts, Mechanisms, and Challenges

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Reversible Photoisomerization of Norbornadiene‐Quadricyclane within a Confined Capsule^†