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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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Time-resolved laser-flash photolysis Faraday rotation spectrometer: a new tool for total OH reactivity measurement and free radical kinetics research
摘要： The total OH reactivity (k’OH) is an important parameter for quantitative assessment of the atmospheric oxidation capacity. Although laboratory measurement of k’OH has been achieved 20 years ago, the instruments required are often costly and complex. Long-term atmospheric observations remain challenging and elusive. In this work, a novel instrument combining laser-flash photolysis with a mid-infrared Faraday rotation spectrometer (LFP-FRS) has been developed for the measurement of k’OH and for studying gas phase free radical kinetics. The reactor is composed of a Herriott-type optical multipass cell, and OH radicals were generated by flash photolysis of ozone with a 266 nm pulsed Nd:YAG laser. The decay of the OH signal was directly measured with a time-resolved FRS spectrometer at 2.8 μm. The overlapping pathlength between the pump beam and probe beam was 25 m. High performance was achieved by subtracting the signals before and after flash photolysis to eliminate interferences caused by H2O absorption and background drift. The optimum precisions (1σ) of OH concentration and k’OH measurement were 4×106 molecule cm-3 and 0.09 s-1 over data acquisition times of 56 s and 112 s, respectively. The performance of the system was evaluated by the reaction of OH with CO and NO. The measured rate coefficients (kOH+CO and kOH+NO) were in good agreement with values reported in the literature. The developed LFP-FRS provides a new, high precision, and highly selective tool for atmospheric chemistry research of OH radicals and other transient paramagnetic free radicals such as HO2 radicals.
关键词： atmospheric oxidation capacity,total OH reactivity,laser-flash photolysis,free radical kinetics,Faraday rotation spectrometer
更新于2025-09-19 17:13:59
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A Second-Generation Chameleon N-Heterocyclic Carbene–Borane Coinitiator for the Visible-Light Oxygen-Resistant Photopolymerization of Both Organic and Water-Compatible Resins
摘要： N-Heterocyclic carbene?boranes (NHC-boranes, NHCBs) were recently described as efficient coinitiators for the visible light photopolymerization of hydroxyethyl methacrylate (HEMA) in the presence of water. In this work, a new, more water-soluble, NHC-borane—2,4-dimethyl-1,2,4,5-tetrazol-3-ylidene borane—has been synthesized, and its efficiency in three-component systems (dye (Acridine Orange), disulfide, and NHC-borane coinitiators) for the polymerization of methacrylate resins under visible light under air has been studied. In fluid resins this new photoinitiating system (PIS) gives better results than the one previously studied. More importantly, this system is competitive with the widely used type II system—camphorquinone/4-(dimethylamino)benzonitrile (DMABN)—for the polymerization of methacrylate resins but better for the photopolymerization of poly(2-hydroxyethyl methacrylate) leading to hydrogels, where the former PIS fails. The excellent ability of the NHC-boranes, and especially the new one, to be used as photopolymerization coinitiators has been analyzed by laser flash photolysis (LFP). The rate constants for elementary reactions of the three boranes and their derived NHC-boryl radicals obtained by LFP correlated well with the molecular modeling data and show that the key for the observed reactivity is the ability of the tetrazolydinyl NHC-borane to repair the peroxyl radicals formed by the reactions of the macroradicals with oxygen.
关键词： laser flash photolysis,methacrylate resins,N-Heterocyclic carbene?boranes,hydrogels,visible light photopolymerization
更新于2025-09-09 09:28:46