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Esters of 4-nitrocinnamic acids and 4-halogene-4’-hydroxyazobenzenes – synthesis, mesogenic and optical studies
摘要： Six new compounds were synthesized that have no alkyl chains in their structure: 4-nitrocinnonates of 4-hydroxyazobenzene, 4-nitro-4'-hydroxyazobenzene, 4-fluoro-4'-hydroxyazobenzene, 4-chloro-4'-hydroxyazobenzene, 4-bromo-4'-hydroxyazobenzene, and 4-iodo-4'-hydroxyazobenzene. Using the polarizing microscopy and differential scanning calorimetry, enthalpies and temperatures of phase transitions were determined. All investigated compounds have an enantiotropic nematic phase. These compounds proved to be extremely thermally stable. Thermal decomposition was observed in temperatures above 300°C. Investigated compounds contain two different chromophore groups (i.e. azo and ethene moieties), which influenced the complex trans–cis isomerization processes of both groups (three time-separated processes were observed). It was shown that the presence of the ethene group significantly shifts the π-π* band towards higher energies. The substituent polarity in the azo group also affected the energy of this absorption band. A weak luminescence effect was observed in the 4-nitrocinnonates of 4-hydroxyazobenzene compound.
关键词： nematic,luminescence,Azobenzenes,trans–cis isomerization,polarizing microscopy,DSC calorimetry
更新于2025-09-23 15:23:52
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Mechanism of the Laser Flash Photolysis of Rydimeric e-Tautomers of 4-N,N-Diethylaminoazobenzene in a 2-Propanol Medium
摘要： Difference transit absorption spectra (TASes) obtained via flash photolysis of isopropanol solutions of 4-N,N-diethylaminoazobenzene (DEAB) using 15 ns laser pulses at wavelengths of λex = 265 and 353 nm are analyzed. The inconsistency of constructing the mechanism of trans (t) → cis (c) photisomerization of DEAB based on the concept of this dye having a monomeric structure is shown. Based on the rydimeric concept of aminoazobenzene dyes, which include Rydberg dimers DEAB2, an adequate explanation is given of the nature of TAS signals with structures that change dramatically when in wavelength λex is altered. TAS signals of DEAB2 are compared to ultrahigh-speed (subpico- and pico-second) TAS signals of rydimers of a reference aminoazobenzene (AAB2) dye. It is established that the main difference between the structures of DEAB2 TAS signals generated by pulses with indicated wavelengths λex is due to the excitation of various rydimeric e-tautomers. In addition, a rydimeric e-tautomer that is unstable in the ground state acquires increased stability in propanol and, by absorbing radiation with λex = 353 nm, alters the structure of one of its monomers to quinoid while remaining a rydimer. It is shown that when excited with radiation pulses at λex = 265 nm, a rydimeric e-tautomer (which is more stable in the ground state) dissociates into individual monomers, one of which isomerizes to form cis-DEAB molecules.
关键词： diethylaminoazobenzene rydimers,rydimer photonics,laser flash photolysis,trans–cis isomerization,visible laser spectroscopy
更新于2025-09-23 15:21:01
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Electronic State and Photophysics of 2-Ethylhexyl-4-methoxycinnamate as UV-B Sunscreen under Jet-Cooled Condition
摘要： The title compound, 2-ethylhexyl-4-methoxycinnamate (2EH4MC), is known as a typical ingredient of sunscreen cosmetics that effectively converts the absorbed UV-B light to thermal energy. This energy conversion process includes the nonradiative decay (NRD): trans?cis isomerization and finally going back to the original structure with a release of thermal energy. In this study, we performed UV spectroscopy for jet-cooled 2EH4MC to investigate the electronic/geometrical structures as well as the NRD mechanism. Laser-induced-fluorescence (LIF) spectroscopy gave the well-resolved vibronic structure of the S1?S0 transition; UV?UV hole-burning (HB) spectroscopy and density functional theory (DFT) calculations revealed the presence of syn and anti isomers, where the methoxy (?OCH3) groups orient in opposite directions to each other. Picosecond UV?UV pump?probe spectroscopy revealed the NRD process from the excited singlet (S1 (1ππ*)) state occurs at a rate constant of ～1010?1011 s?1, attributed to internal conversion (IC) to the 1nπ* state. Nanosecond UV?deep UV (DUV) pump?probe spectroscopy identified a transient triplet (T1 (3ππ*)) state, whose energy (from S0) and lifetime are 18 400 cm?1 and 20 ns, respectively. These results demonstrate that the photoisomerization of 2EH4MC includes multistep internal conversions and intersystem crossings, described as "S1 (trans, 1ππ*) → 1nπ* → T1 (3ππ*) → S0 (cis)".
关键词： nonradiative decay,photophysics,DFT calculations,trans?cis isomerization,jet-cooled spectroscopy,2-ethylhexyl-4-methoxycinnamate,UV-B sunscreen
更新于2025-09-19 17:13:59