期刊
JOURNAL OF MATERIALS CHEMISTRY
卷 22, 期 1, 页码 232-240出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1jm13556b
关键词
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资金
- Research Project Competition of HKUST [RPC11SC09, RPC10SC13]
- Research Grants Council of Hong Kong [604711, 603509, HKUST2/CRF/10]
- University Grants Committee of Hong Kong [AoE/P-03/08]
- National Science Foundation of China [20634020, 20974028]
- Cao Guangbiao Foundation of Zhejiang University
- CONACYT [J49512F]
Luminogenic molecules [(TPE)3 (1), TPE-C = C-TPE-C = C-TPE (2), and TPE-C equivalent to C-TPE-C equivalent to C-TPE (3)] and their polymers P1-P3 are constructed from tetraphenylethene (TPE) building blocks in high yields by Suzuki, Witting, and Sonogashira coupling reactions. All the compounds are soluble and enjoy high thermal stability, losing little of their weights when they are heated to 290-528 degrees C under nitrogen or 288-436 degrees C in air. Analyses by UV spectroscopy and cyclic voltammetry as well as theoretical calculations show that the conjugation of the luminophores is in the order of 2 > 3 > 1, P2 > P3 > P1, and P1-P3 > 1-3. All the molecules and polymers are weakly emissive in solutions. They, however, become strong emitters in the aggregate state with fluorescence quantum yields up to 90%. Both 1-3 and P1-P3 exhibit the feature of aggregation-enhanced two-photon excited fluorescence. Large two-photon absorption cross sections (up to similar to 900 GM) are observed in the nanoaggregates of the polymers. Thin solid films of the polymers show high refractive indices (RI 1.7649 - 1.6873) in a wide wavelength region of 400-1700 nm, high modified Abbe numbers (v(D)' up to 3436), and low optical dispersions (D' down to 2.9 x 10(-4)). The light emissions of the polymers can be quenched exponentially by picric acid with large quenching constants, suggesting that they can be utilized as efficient chemosensors for explosive detection.
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