研究目的
To analyze the photochromic and fluorescence properties of BTD-DTE and DTE-BODIPY conjugates in various solvents to understand their behavior in ground and excited states, and to explore their potential for tuneable on-off fluorescence modulation in optical devices.
研究成果
BTD-DTE exhibits significant solvent-dependent fluorescence modulation, with on-off behavior in less polar solvents and off-on in polar solvents, due to changes in dipole moment and potential TICT states. DTE-BODIPY shows minor solvent effects and is less suitable for read-out due to overlapping emission bands. The findings highlight the potential of BTD-DTE for applications in optical devices with tuneable fluorescence, and suggest further time-resolved studies to understand excited state processes.
研究不足
The study is limited to in-solution experiments; future work on semiconductor surfaces (e.g., TiO2) is planned but not included. The comparative method for fluorescence quantum yield determination is not precise for broad emission characteristics. Solvent viscosity effects on ring closure were not investigated. The excitation wavelength for ring closure (345 nm) is not ideal and may cause decomposition. Only a limited range of solvents was tested, and protic solvents like MeOH may exhibit different behaviors due to hydrogen bonding.
1：Experimental Design and Method Selection:
The study involved in-solution spectroscopic analysis of photochromic diarylethene-fluorophore conjugates (BTD-DTE and DTE-BODIPY) to investigate their photoisomerization and fluorescence properties in solvents of varying polarity and proticity. Theoretical models such as Lippert-Mataga plots were used to analyze solvent effects on Stokes shifts and quantum yields.
2：Sample Selection and Data Sources:
Samples were prepared as diluted solutions (e.g., 1.8?10-5 M) in different solvents including toluene, dioxane, MTBE, EtOAc, DCM, DMSO, MeCN, and MeOH. Data were acquired through UV/Vis and fluorescence spectroscopy.
3：8?10-5 M) in different solvents including toluene, dioxane, MTBE, EtOAc, DCM, DMSO, MeCN, and MeOH. Data were acquired through UV/Vis and fluorescence spectroscopy.
List of Experimental Equipment and Materials:
3. List of Experimental Equipment and Materials: Equipment included UV/Vis spectrometer (AvaSpec Dual-channel with AvaLight-DH-S-BAL light source), fluorescence spectrometer (F-4500 FL, Hitachi), LEDs for irradiation (Thorlabs 345 nm and 632 nm), cuvettes (1 cm), and degassing setup with argon. Materials included the synthesized conjugates BTD-DTE and DTE-BODIPY, and solvents.
4：Experimental Procedures and Operational Workflow:
Solutions were degassed with argon for 10 minutes in an ultrasonic bath. Photoisomerization was induced by irradiating with 345 nm or 632 nm LEDs while stirring, and absorbance changes were recorded. For fluorescence measurements, samples were prepared at pss (photostationary state) by UV irradiation, diluted, and emission spectra were recorded with baseline correction and sensitivity adjustment. Quantum yields were determined using the comparative method with tetramethyl-BODIPY and rhodamine 101 as standards.
5：Data Analysis Methods:
Data analysis included calculation of extinction coefficients, Stokes shifts, quantum yields (φOC, φCO, φFl), and Lippert-Mataga plots to correlate solvent polarity with spectroscopic changes. Statistical methods were not explicitly mentioned, but trends were analyzed from the collected data.
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