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

IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL
Sofya A. Dogadaeva , Lubov A. Antina , Alexander A. Ksenofontov , Alexander A. Kalyagin , Lubov V. Frantsuzova , Olga A. Lodochnikova , Mikhail B. Berezin , Elena V. Antina
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引用次数: 0

摘要

能够通过系统间交叉(ISC)过程形成三重态激发态的重原子游离BODIPY光敏剂小分子对于从生物医学到光催化等各种技术至关重要。本文比较分析了四甲基和五甲基取代的BODIPY染料(1-6)在不同有机溶剂溶液中的光敏效果。在分子结构中缺少重元素原子和供体取代基的情况下,α-未取代的BODIPY发光团能够通过系统间交叉(ISC)过程形成三重态激发态。对四甲基和五甲基取代的BODIPY激发态的DFT计算分析表明,甲基取代的位置对ΔES-T值和三态能量转移效率以及1-6染料的光敏效率起主要作用。首次证明了α,α-未取代的BODIPY 1在各种天然有机溶剂溶液中具有良好的有效吸收(logε为4.55 ~ 4.64),荧光(Փfl为47% ~ 66%)和单重态产氧(ΦΔ为14% ~ 40%),长荧光寿命(τfl为5.75 ~ 6.13 ns)和小Stokes位移(212 ~ 537 cm−1),并且分子小,合成简单。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

A new method to create heavy-atom free small molecule photosensitizers based on α-unsubstituted BODIPY dyes

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 (16) 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 16 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.
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来源期刊
Journal of Molecular Liquids
Journal of Molecular Liquids 化学-物理:原子、分子和化学物理
CiteScore
10.30
自引率
16.70%
发文量
2597
审稿时长
78 days
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.
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