研究目的
To investigate the photonics of complexes of p- and d-elements with dipyrromethenates, focusing on the role of substituents, medium, and complexing agents, and to explore their applications as laser active media, oxygen sensors, and photosensitizers for singlet oxygen generation.
研究成果
Alkyl-, cycloalkyl-, phenyl-, benzyl-, and meso-propargylamino-substituted difluoroborates of dipyrromethenes are efficient photostable laser active media for the visible range. Halogenated BODIPY and Zn complexes serve as sensor media for oxygen concentration detection and photosensitizers for singlet oxygen generation in PDT and photocatalytic reactions. Photostability is sufficient for optical device applications, with ongoing research needed to explain anomalies in heavy atom effects.
研究不足
The study is limited to specific dipyrromethenate compounds and solvents/matrices used; photostability varies with substituents and irradiation conditions. Quantum-chemical models may have approximations, and some photophysical behaviors (e.g., in halogenated derivatives) require further investigation.
1：Experimental Design and Method Selection:
The study involved synthesizing and characterizing dipyrromethenate complexes, using spectral-luminescent measurements, lasing experiments, sensor testing, and photosensitization studies. Quantum-chemical calculations were employed to support experimental findings.
2：Sample Selection and Data Sources:
Compounds were synthesized at the Institute of Solution Chemistry of the RAS, with solvents like ethanol, butanol, acetonitrile, toluene, cyclohexane, ethyl acetate (HPLC grade), and solid matrices (PMMA, POSS-polymer, methylcellulose).
3：List of Experimental Equipment and Materials:
Spectrometers (CM2203, Cary Eclipse, FLSP95), lasers (Nd:YAG LQ129, LQ529B, Ti:Sapphire amplifier), energy meters (OPHIR NOVA, Gentec E100), spectrometers (AVANTES), cryostat (Optistat DN), and materials for synthesis and measurements.
4：Experimental Procedures and Operational Workflow:
Measured absorption, fluorescence, phosphorescence spectra, lifetimes, quantum yields, lasing characteristics with laser excitation, sensor properties with gas mixtures, and singlet oxygen generation using DPBF trap. Flash photolysis and pump-probe methods were used for transient absorption studies.
5：Data Analysis Methods:
Data analyzed using reference methods for quantum yields, Stern-Volmer plots for sensor characteristics, and quantum-chemical computations (INDO method, B3LYP functional with def2-TZVP basis) for electronic structure analysis.
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FLSP95 spectrophotometer
FLSP95
Edinburgh Instruments
Measuring fluorescence lifetimes at pico- and nanosecond intervals.
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OPHIR NOVA energy meter
OPHIR NOVA
OPHIR
Measuring energies of lasing and pump radiation.
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CM2203 spectrometer
CM2203
SOLAR
Measuring spectral-luminescent properties including absorption and fluorescence spectra.
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Cary Eclipse spectrometer
Cary Eclipse
Varian
Measuring spectral-luminescent properties.
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Nd:YAG laser
LQ129
SOLAR
Excitation for lasing characteristics with second harmonic at 532 nm.
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Nd:YAG laser
LQ529B
SOLAR
Excitation for lasing characteristics with third harmonic at 355 nm.
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Ti:Sapphire amplifier
Excitation for pump-probe method with second harmonic at 400 nm.
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Gentec E100 energy meter
Gentec E100
Gentec
Measuring energies of lasing and pump radiation.
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AVANTES laser spectrometer
AVANTES
Measuring spectral lasing characteristics.
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Optistat DN cryostat
Optistat DN
Cooling for measurements with the Cary Eclipse spectrometer.
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