Sofya A. Dogadaeva , Lubov A. Antina , Alexander A. Ksenofontov , Alexander A. Kalyagin , Lubov V. Frantsuzova , Olga A. Lodochnikova , Mikhail B. Berezin , Elena V. Antina
{"title":"基于α-未取代BODIPY染料制备无重原子小分子光敏剂的新方法","authors":"Sofya A. Dogadaeva , Lubov A. Antina , Alexander A. Ksenofontov , Alexander A. Kalyagin , Lubov V. Frantsuzova , Olga A. Lodochnikova , Mikhail B. Berezin , Elena V. Antina","doi":"10.1016/j.molliq.2025.128608","DOIUrl":null,"url":null,"abstract":"<div><div>Heavy-atom free BODIPY photosensitizer small molecules capable of forming triplet excited states <em>via</em> the intersystem crossing (ISC) process are critically important for various technologies: from biomedicine to photocatalysis. In this paper a comparative analysis of tetra- and pentamethyl-substituted BODIPY dyes (<strong>1</strong>–<strong>6</strong>) photosensitizing efficiency in various organic solvents solutions are presented. α-Unsubstituted BODIPY luminophores ability to forming triplet excited states <em>via</em> the intersystem crossing (ISC) process in the absence of heavy element atoms and donor substituents in the molecular structure has been demonstrated. Analysis of DFT calculations of tetramethyl- and pentamethyl-substituted BODIPY excited states showed, that the position of methyl substitutions plays major roles on the ΔE<sub>S-T</sub> value and the efficiency of energy transfer to the triplet state and, accordingly, the photosensitization efficiency of <strong>1</strong>–<strong>6</strong> dyes. For the first time it has been shown that α,α-unsubstituted BODIPY <strong>1</strong> has a favorable combination of effective absorption (log<em>ε</em> from 4.55 to 4.64), fluorescence (<em>Փ</em><sub>fl</sub> varies from 47 to 66 %) and singlet oxygen generation (<em>Φ</em><sub>Δ</sub> varies from 14 to 40 %), long fluorescence lifetimes (<em>τ</em><sub>fl</sub> from 5.75 to 6.13 ns) and small Stokes shift (212 to 537 cm<sup>−1</sup>) in various nature organic solvent solutions along with the small molecule size and synthesis simplicity.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"437 ","pages":"Article 128608"},"PeriodicalIF":5.2000,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A new method to create heavy-atom free small molecule photosensitizers based on α-unsubstituted BODIPY dyes\",\"authors\":\"Sofya A. Dogadaeva , Lubov A. Antina , Alexander A. Ksenofontov , Alexander A. Kalyagin , Lubov V. Frantsuzova , Olga A. Lodochnikova , Mikhail B. Berezin , Elena V. Antina\",\"doi\":\"10.1016/j.molliq.2025.128608\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Heavy-atom free BODIPY photosensitizer small molecules capable of forming triplet excited states <em>via</em> the intersystem crossing (ISC) process are critically important for various technologies: from biomedicine to photocatalysis. In this paper a comparative analysis of tetra- and pentamethyl-substituted BODIPY dyes (<strong>1</strong>–<strong>6</strong>) photosensitizing efficiency in various organic solvents solutions are presented. α-Unsubstituted BODIPY luminophores ability to forming triplet excited states <em>via</em> the intersystem crossing (ISC) process in the absence of heavy element atoms and donor substituents in the molecular structure has been demonstrated. Analysis of DFT calculations of tetramethyl- and pentamethyl-substituted BODIPY excited states showed, that the position of methyl substitutions plays major roles on the ΔE<sub>S-T</sub> value and the efficiency of energy transfer to the triplet state and, accordingly, the photosensitization efficiency of <strong>1</strong>–<strong>6</strong> dyes. For the first time it has been shown that α,α-unsubstituted BODIPY <strong>1</strong> has a favorable combination of effective absorption (log<em>ε</em> from 4.55 to 4.64), fluorescence (<em>Փ</em><sub>fl</sub> varies from 47 to 66 %) and singlet oxygen generation (<em>Φ</em><sub>Δ</sub> varies from 14 to 40 %), long fluorescence lifetimes (<em>τ</em><sub>fl</sub> from 5.75 to 6.13 ns) and small Stokes shift (212 to 537 cm<sup>−1</sup>) in various nature organic solvent solutions along with the small molecule size and synthesis simplicity.</div></div>\",\"PeriodicalId\":371,\"journal\":{\"name\":\"Journal of Molecular Liquids\",\"volume\":\"437 \",\"pages\":\"Article 128608\"},\"PeriodicalIF\":5.2000,\"publicationDate\":\"2025-09-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Liquids\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0167732225017854\",\"RegionNum\":2,\"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 Molecular Liquids","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0167732225017854","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A new method to create heavy-atom free small molecule photosensitizers based on α-unsubstituted BODIPY dyes
Heavy-atom free BODIPY photosensitizer small molecules capable of forming triplet excited states via the intersystem crossing (ISC) process are critically important for various technologies: from biomedicine to photocatalysis. In this paper a comparative analysis of tetra- and pentamethyl-substituted BODIPY dyes (1–6) photosensitizing efficiency in various organic solvents solutions are presented. α-Unsubstituted BODIPY luminophores ability to forming triplet excited states via the intersystem crossing (ISC) process in the absence of heavy element atoms and donor substituents in the molecular structure has been demonstrated. Analysis of DFT calculations of tetramethyl- and pentamethyl-substituted BODIPY excited states showed, that the position of methyl substitutions plays major roles on the ΔES-T value and the efficiency of energy transfer to the triplet state and, accordingly, the photosensitization efficiency of 1–6 dyes. For the first time it has been shown that α,α-unsubstituted BODIPY 1 has a favorable combination of effective absorption (logε from 4.55 to 4.64), fluorescence (Փfl varies from 47 to 66 %) and singlet oxygen generation (ΦΔ varies from 14 to 40 %), long fluorescence lifetimes (τfl from 5.75 to 6.13 ns) and small Stokes shift (212 to 537 cm−1) in various nature organic solvent solutions along with the small molecule size and synthesis simplicity.
期刊介绍:
The journal includes papers in the following areas:
– Simple organic liquids and mixtures
– Ionic liquids
– Surfactant solutions (including micelles and vesicles) and liquid interfaces
– Colloidal solutions and nanoparticles
– Thermotropic and lyotropic liquid crystals
– Ferrofluids
– Water, aqueous solutions and other hydrogen-bonded liquids
– Lubricants, polymer solutions and melts
– Molten metals and salts
– Phase transitions and critical phenomena in liquids and confined fluids
– Self assembly in complex liquids.– Biomolecules in solution
The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include:
– Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.)
– Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.)
– Light scattering (Rayleigh, Brillouin, PCS, etc.)
– Dielectric relaxation
– X-ray and neutron scattering and diffraction.
Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.