研究目的
To develop photostable triplet photosensitizers based on palladium calix[6]phyrin complexes for efficient singlet oxygen generation, particularly for applications like photodynamic therapy.
研究成果
The synthesized palladium calix[6]phyrin complexes exhibit broad absorption in the visible-to-NIR region, appropriate triplet energy, and long lifetimes, making them efficient and photostable sensitizers for singlet oxygen generation. The number of metal cations and coordination environment significantly influence their properties. These complexes are promising for applications like photodynamic therapy and photocatalysis.
研究不足
The paper does not explicitly state limitations, but potential areas include the complexity of synthesis, possible instability of some complexes under irradiation (e.g., 2-Pd-H2 showed degradation), and the need for further studies on the effect of coordination environments on excited state dynamics.
1：Experimental Design and Method Selection:
The study involved synthesizing mono- and bis-palladium complexes of doubly N-confused calix[6]phyrins, characterizing them using various spectroscopic and crystallographic methods, and evaluating their photophysical properties and singlet oxygen generation efficiency. Theoretical calculations (DFT and TD-DFT) were used to support experimental findings.
2：Sample Selection and Data Sources:
Freebase calix[6]phyrin ligands (1 and 2) were synthesized as precursors. Palladium complexes were prepared using Pd(OAc)2 under reflux conditions in CH2Cl2/MeOH mixtures.
3：List of Experimental Equipment and Materials:
Instruments included NMR spectrometers (JEOL ECX500), UV-Vis-NIR spectrometer (Shimadzu UV-3150PC), fluorescence spectrometer (SPEX Fluorolog-3-NIR), EPR spectrometer, X-ray diffractometer (Rigaku Saturn), and computational software (Gaussian16). Materials included Pd(OAc)2, solvents (CH2Cl2, MeOH, toluene), and reagents like 1,5-dihydroxynaphthalene (DHN) and spin traps (TEMP, DMPO).
4：6). Materials included Pd(OAc)2, solvents (CH2Cl2, MeOH, toluene), and reagents like 1,5-dihydroxynaphthalene (DHN) and spin traps (TEMP, DMPO). Experimental Procedures and Operational Workflow:
4. Experimental Procedures and Operational Workflow: Synthesis involved refluxing ligands with Pd(OAc)2, purification by column chromatography. Characterization included NMR, UV-Vis-NIR, emission spectroscopy, cyclic voltammetry, X-ray crystallography, and EPR measurements. Singlet oxygen quantum yields were determined using DHN oxidation under photoirradiation with a Xe lamp.
5：Data Analysis Methods:
Data were analyzed using software like Gaussian16 for DFT calculations, and spectroscopic data were processed to determine parameters such as absorption coefficients, quantum yields, and lifetimes.
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NMR Spectrometer
ECX500
JEOL
Recording 1H and 19F NMR spectra for structural characterization of complexes.
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UV-Vis-NIR Spectrometer
UV-3150PC
Shimadzu
Measuring absorption spectra in the ultraviolet-visible-near infrared region.
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Fluorescence Spectrometer
Fluorolog-3-NIR
HORIBA
Recording fluorescence and phosphorescence spectra, including singlet oxygen emission.
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X-ray Diffractometer
Saturn
Rigaku
Performing single-crystal X-ray structural analysis.
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Photomultiplier Tube
R5509
Hamamatsu
Detecting near-infrared emissions in fluorescence measurements.
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Time-Correlated Single Photon Counting System
Measuring phosphorescence lifetimes.
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Xe Lamp
300 W
Providing light irradiation for singlet oxygen generation experiments.
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Laser
Nd:YAG
Excitation source for time-resolved emission spectroscopy.
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