Journal
JOURNAL OF MATERIALS CHEMISTRY A
Volume 5, Issue 27, Pages 14343-14354Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7ta04351a
Keywords
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Funding
- National Natural Science Foundation of China [21276149, 21376125]
- Program for Scientific research innovation team in Colleges and universities of Shandong Province
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A three-dimensional hyperbranched polymer (3D-HP) with sigma-pi conjugated PDMPS (poly(dichloromethylphenylsilane)s) units covalently bonded to a polyhedral oligosilsesquioxane (POSS) scaffold was prepared by a one-step thiol-ene click chemistry reaction. Compared with POSS-based organic polymers, the 3D-HP with a flexible Si-Si chain showed enhanced solubility. This 3D hyperbranched polymer exhibited outstanding thermal stability and optimal photophysical properties. For probing nitroaromatics (NACs), the 3D-HP showed excellent sensitivity (K-sv = 2.83 x 10(4) M-1) against the presence of a tetrahydrofuran (THF) solution of 2,4,6-trinitrotoluene (TNT). In addition, the 3D-HP coated on glass films exposed to saturated DNT vapor exhibited a high quenching efficiency (eta(EP)) of the fluorescence of 3D-HP film, which was drastically suppressed (82%) for 300 s. The excellent fluorescent quenching performance of the 3D-HP can be attributed to the following points: (i) hyperbranched conjugated polymers afford multi-dimensional transport pathways for excitons migration; (ii) there exists in the polymer high electron affinity and rapid electron delocalization of sigma-pi conjugated polysilanes; (iii) noncovalent interactions between the electropositive delta(+) Si atoms of sigma-pi conjugated polysilanes and N and/or O atoms of electron-deficient nitroaromatics (NACs) facilitate the adsorption of NACs. Furthermore, the bulky octathiol-POSS units in the 3D-HP can improve the permeability of the film sensor. This 3D hyperbranched sigma-pi conjugated polymer 3D-HP has the potential to be used to prepare sensitive, selective, and stable sensors for the detection of NACs explosives.
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