研究目的
To synthesize and characterize phosphino bridged dinuclear Cu(I) complexes with arylazoimidazole ligands, and to study their photochromic properties, including trans-to-cis isomerization under UV light and thermal cis-to-trans isomerization.
研究成果
The synthesized phosphino bridged dinuclear Cu(I) complexes exhibit photochromic behavior with trans-to-cis isomerization under UV light, showing lower rates and quantum yields compared to free ligands due to increased molecular weight. Thermal cis-to-trans isomerization has lower activation energy in complexes. Structural confirmation via X-ray diffraction supports the coordination geometry, and the complexes are stable under repeated irradiation.
研究不足
The study is limited to specific Cu(I) complexes with arylazoimidazole ligands in methanol solution; it may not generalize to other solvents or metal complexes. The photoisomerization rates are dependent on molecular mass and steric factors, which could be optimized. The mechanism assumes bond cleavage, but direct evidence is not provided.
1：Experimental Design and Method Selection:
The study involved synthesizing dinuclear Cu(I) complexes using 1-alkyl-2-(arylazo)imidazole ligands and bis(diphenylphosphino)methane as a bridge. Methods included spectral analysis (UV-Vis, IR, 1H-NMR) and single crystal X-ray diffraction for structural confirmation. Photochromism was studied by irradiating with UV light and monitoring spectral changes.
2：Sample Selection and Data Sources:
Ligands were synthesized following reported procedures, and complexes were prepared in methanol under nitrogen atmosphere. Samples included various RaaiR/ ligands and their Cu(I) complexes.
3：List of Experimental Equipment and Materials:
Equipment included Perkin-Elmer 2400 CHNS/O elemental analyzer, Perkin Elmer Lambda 25 spectrophotometer, Perkin Elmer RX-1 FTIR spectrophotometer, Perkin Elmer LS-55 spectrofluorimeter, Bruker (AC) 300 MHz FTNMR spectrometer, CrysAlis CCD diffractometer with Mo-Kα radiation, and Solar Simulator ISS P110 lamp. Materials included [Cu(CH3CN)4]ClO4, dppm, and purified solvents.
4：Experimental Procedures and Operational Workflow:
Synthesis involved adding ligand solutions to [Cu(CH3CN)4]ClO4 and dppm in methanol under nitrogen, stirring, filtering, and crystallizing. Spectral data were collected, and photoisomerization was induced by UV irradiation at 365 nm, with rates and quantum yields measured using spectrophotometry.
5：Data Analysis Methods:
Data were analyzed using software like SAINT, SHELXL-97, SHELXS-97, PLATON, and ORTEP-3 for crystallography. Quantum yields were calculated using standard equations, and activation energies were derived from Arrhenius plots.
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