関連する実験動画
Updated: Jun 19, 2026

09:33
Determination of the Photoisomerization Quantum Yield of a Hydrazone Photoswitch
Published on: February 7, 2022
ブリッジ付きアゾベンゼンの高度に効率的な可逆Z-E光イソメリゼーションは,解像度S(1)(n pi*) の吸収帯を通って可視光を通す
Ron Siewertsen1, Hendrikje Neumann, Bengt Buchheim-Stehn
1Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstr. 40, D-24098 Kiel, Germany.
Journal of the American Chemical Society
|October 16, 2009
まとめ
この研究では,制約された橋渡しのアゾベンゼン誘導体のZ-E光スイッチを調査しています. その好ましい光染色特性により,特に低温で有望な分子フォトスイッチとなります.
科学分野:
- フォトケミストリー フォトケミストリー
- 有機化学 オーガニック・ケミストリー
- マテリアルサイエンス 材料科学
背景:
- アゾベンゼン誘導体は,そのフォトスイッチング能力のために広く研究されています.
- 制限された分子構造は,光化学的性質を大幅に変化させることができます.
- 構造と性質の関係を理解することは,高度な分子スイッチの設計の鍵です.
研究 の 目的:
- 厳しく制限された橋渡しアボベンゼン誘導体である5,6-ジヒドロディベンゾ[c,g][1,2]ディアゾシン (1) の可逆的なZ-Eフォトスイッチング特性を調査する.
- フォトクロミックな性質を定量的に評価し,通常のアゾベンゼン (AB) と比較する.
- 分子フォトスイッチとしてのその可能性を評価するために.
主な方法:
- 紫外線/紫外線吸収スペクトロスコーピーは,n-ヘキサン溶液で実施する.
- Z-Eイソメリゼーション効率と量子収量に関する定量分析.
- E同位体の熱寿命の測定. E同位体の熱寿命の測定.
主要な成果:
- 化合物 (1) は,lambda(Z) = 404 nmとlambda(E) = 490 nmで,S(1)(n pi*) 吸収帯が十分に分離されていることを示しています.
- 385nmの光を使用した1Zから1E (ガンマ=92 +/- 3%) への高いスイッチング効率.
- 1Eから1Zへの効率的なバックスイッチング (約. 100%の収量) で,520nmの光を使用しています.
- 量子収量: Phi(Z-->E) = 72 +/- 4%,そして Phi(E-->Z) = 50 +/- 10%.
- E同位体は,温度28.5°Cで4.5 +/- 0.1hの熱寿命を持っています.
結論:
- 制約された橋渡しアゾベンゼン誘導体 (1) は,通常のアゾベンゼンよりも著しく有利な光染色および光スイッチング特性を示しています.
- エチレンブリッジの制約は,Z-Eフォトイソメリゼーション反応を阻害するのではなく,強化する.
- この化合物は,特に低温での分子フォトスイッチアプリケーションの有望な候補です.
関連する概念動画
Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
The Z-Scheme of Electron Transport in Photosynthesis
The light reactions of photosynthesis assume a linear flow of electrons from water to NADP+. During this process, light energy drives the splitting of water molecules to produce oxygen. However, oxidation of water molecules is a thermodynamically unfavorable reaction and requires a strong oxidizing agent. This is accomplished by the first product of light reactions: oxidized P680 (or P680+), the most powerful oxidizing agent known in biology. The oxidized P680 that acquires an electron from the...
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Photosystem I
Although structurally similar to photosystem II (PSII), photosystem I (PSI) is has a different electron supplier and electron acceptor.
Both these photosystems work in concert. An excited electron from PSII is relayed to PSI via an electron transport chain in the thylakoid membrane of the chloroplast, which is comprised of the carrier molecule plastoquinone, the dual-protein cytochrome complex, and plastocyanin. As electrons move between PSII and PSI, they lose energy and must be re-energized...
Both these photosystems work in concert. An excited electron from PSII is relayed to PSI via an electron transport chain in the thylakoid membrane of the chloroplast, which is comprised of the carrier molecule plastoquinone, the dual-protein cytochrome complex, and plastocyanin. As electrons move between PSII and PSI, they lose energy and must be re-energized...
Deactivation Processes: Jablonski Diagram
Luminescence, the emission of light by a substance that has absorbed energy, is a process that involves the interaction of molecules with light. The energy-level diagram, or Jablonski diagram, is a graphical representation of these interactions, illustrating the various states and transitions a molecule can undergo. In a typical Jablonski diagram, the lowest horizontal line represents the ground-state energy of the molecule, which is usually a singlet state. This state represents the energies...
Cycloaddition Reactions: MO Requirements for Photochemical Activation
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
