Detection of nitroaromatic explosives by a 3D hyperbranched σ-π Conjugated polymer based on a POSS scaffold

A three-dimensional hyperbranched polymer (3D-HP) with σ-π 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 × 10⁴ 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 (η_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 σ-π conjugated polysilanes; (iii) noncovalent interactions between the electropositive δ⁺ Si atoms of σ-π 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 σ-π conjugated polymer 3D-HP has the potential to be used to prepare sensitive, selective, and stable sensors for the detection of NACs explosives.