{"title":"偶氮化合物顺式异构体在n−π *波段各向同性吸收的实验证据","authors":"S. Grebenkin, V.M. Syutkin","doi":"10.1016/j.jphotochem.2025.116509","DOIUrl":null,"url":null,"abstract":"<div><div>Polymeric materials and molecular glasses containing azo moieties have been the subject of many investigations due to the light driven behavior of such materials. The primary photochemical process in these systems is the light-induced <em>trans-cis</em> isomerization of azo moieties. It is commonly accepted that the <em>trans</em> molecules of azo chromophores absorb light by dipole mechanism, i.e., proportionally to the square cosine of the angle between the transition dipole moment and the light polarization. However, there is no consensus regarding the anisotropy of the absorption cross section of <em>cis</em> molecules. In this study, <em>p</em>-azotoluene (AT) and 1-naphthyl-<em>p</em>-azo-methoxybenzene (NAMB) dissolved in <em>ortho</em>-terphenyl (OTP) are irradiated with linearly polarized light in the region of the <span><math><mrow><mi>n</mi><mo>−</mo><msup><mrow><mi>π</mi></mrow><mrow><mo>∗</mo></mrow></msup></mrow></math></span> absorption band in a wide temperature range including the glass transition temperature of OTP, <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span>. Upon irradiation, the <em>trans-cis</em> isomerization and the reorientation of azo chromophores occur. Near <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span>, a kink in temperature dependence of the photostationary absorbance is observed. This fact together with modeling the time profiles of absorbance and anisotropy lead us to conclude that <em>cis</em> molecules of both azo chromophores absorb light isotropically upon irradiation in the <span><math><mrow><mi>n</mi><mo>−</mo><msup><mrow><mi>π</mi></mrow><mrow><mo>∗</mo></mrow></msup></mrow></math></span> absorption band.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116509"},"PeriodicalIF":4.7000,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"An experimental evidence for the isotropic absorption by cis isomers of azo compounds in the n−π∗ band\",\"authors\":\"S. Grebenkin, V.M. Syutkin\",\"doi\":\"10.1016/j.jphotochem.2025.116509\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Polymeric materials and molecular glasses containing azo moieties have been the subject of many investigations due to the light driven behavior of such materials. The primary photochemical process in these systems is the light-induced <em>trans-cis</em> isomerization of azo moieties. It is commonly accepted that the <em>trans</em> molecules of azo chromophores absorb light by dipole mechanism, i.e., proportionally to the square cosine of the angle between the transition dipole moment and the light polarization. However, there is no consensus regarding the anisotropy of the absorption cross section of <em>cis</em> molecules. In this study, <em>p</em>-azotoluene (AT) and 1-naphthyl-<em>p</em>-azo-methoxybenzene (NAMB) dissolved in <em>ortho</em>-terphenyl (OTP) are irradiated with linearly polarized light in the region of the <span><math><mrow><mi>n</mi><mo>−</mo><msup><mrow><mi>π</mi></mrow><mrow><mo>∗</mo></mrow></msup></mrow></math></span> absorption band in a wide temperature range including the glass transition temperature of OTP, <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span>. Upon irradiation, the <em>trans-cis</em> isomerization and the reorientation of azo chromophores occur. Near <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span>, a kink in temperature dependence of the photostationary absorbance is observed. This fact together with modeling the time profiles of absorbance and anisotropy lead us to conclude that <em>cis</em> molecules of both azo chromophores absorb light isotropically upon irradiation in the <span><math><mrow><mi>n</mi><mo>−</mo><msup><mrow><mi>π</mi></mrow><mrow><mo>∗</mo></mrow></msup></mrow></math></span> absorption band.</div></div>\",\"PeriodicalId\":16782,\"journal\":{\"name\":\"Journal of Photochemistry and Photobiology A-chemistry\",\"volume\":\"469 \",\"pages\":\"Article 116509\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-06-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Photochemistry and Photobiology A-chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1010603025002497\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Photochemistry and Photobiology A-chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1010603025002497","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
An experimental evidence for the isotropic absorption by cis isomers of azo compounds in the n−π∗ band
Polymeric materials and molecular glasses containing azo moieties have been the subject of many investigations due to the light driven behavior of such materials. The primary photochemical process in these systems is the light-induced trans-cis isomerization of azo moieties. It is commonly accepted that the trans molecules of azo chromophores absorb light by dipole mechanism, i.e., proportionally to the square cosine of the angle between the transition dipole moment and the light polarization. However, there is no consensus regarding the anisotropy of the absorption cross section of cis molecules. In this study, p-azotoluene (AT) and 1-naphthyl-p-azo-methoxybenzene (NAMB) dissolved in ortho-terphenyl (OTP) are irradiated with linearly polarized light in the region of the absorption band in a wide temperature range including the glass transition temperature of OTP, . Upon irradiation, the trans-cis isomerization and the reorientation of azo chromophores occur. Near , a kink in temperature dependence of the photostationary absorbance is observed. This fact together with modeling the time profiles of absorbance and anisotropy lead us to conclude that cis molecules of both azo chromophores absorb light isotropically upon irradiation in the absorption band.
期刊介绍:
JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds.
All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor).
The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.