Anionic polymerisation of phosphaalkenes bearing polyaromatic chromophores: phosphine polymers showing "turn-on" emission selectively with peroxide

作者：Rawe Benjamin W; Chun Cindy P; Gates Derek P^*

来源：Chemical Science, 2014, 5(12): 4928-4938.

DOI：10.1039/c4sc02133a

Three new phosphaalkenes bearing C-aryl chromophores, MesP = CPh(Ar) (1a: Ar = 1-naphthyl, 1b: 9-phenanthryl, 1c: 5-dibenzosuberenyl; Mes = 2,4,6-trimethylphenyl), are reported. Each phosphaalkene was characterised by multinuclear NMR spectroscopy (H-1, C-13, P-31), X-ray crystallography, mass spectrometry, UV/Visible spectroscopy and elemental microanalysis (1b and 1c). Monomers 1a and 1b were successfully polymerised using anionic methods of initiation (n-BuLi: 5 and 1.5 mol%, respectively) to afford poly(methylenephosphine)s (PMPs: 2a: M-n = 15 100 Da, PDI = 1.14; 2b: M-n = 17 500 Da; PDI = 1.39). Detailed NMR spectroscopic analysis of polymer 2a revealed that its microstructure is primarily composed of [P(CHPhNaph)-(4,6-Me2C6H2)-2-CH2](n) units rather than the expected [P(Mes)-CPh2](n). Functional polymer 2a was oxidised to the phosphine oxide 2a center dot O or phosphine sulfide 2a center dot S, and coordinated to borane to afford 2a center dot BH3 or gold(I) to afford 2a center dot AuCl. Significantly, 2a shows "turn-on" emission properties selectively as its oxide 2a center dot O (lambda(ex) = 286 nm; lambda(em) = 342 nm) which is prepared by treatment with hydrogen peroxide.

• 出版日期2014