ABSTRACT
We exploit the fluoride that is released via the para-fluoro-thiol reaction (PFTR) to cleave silyl ethers, turning the PFTR into an effective self-reporting chemiluminescence (CL) probe. The cleavage induces chemiluminescence and hence provides an optical read-out for the conversion of the PFTR. The PFTR chemiluminescence read-out is established on small molecule thiols, and subsequently expanded to polymers and networks.
ABSTRACT
Herein, we introduce a fast, additive-free, ambient temperature photochemical approach - utilising the novel Diels-Alder cycloaddition of a photo-active ortho-methylbenzaldehyde (oMBA) with a terminal alkyne - for preparing functional acid-sensitive profluorescent nano-/microspheres in one step. Not previously reported, the possibility of applying such a reaction in the context of particle synthesis provides new possibilities for particle design, where multi-step reactivity can be gated into distinct steps. First, a photochemically-gated particle formation step yields a material possessing a reactive, spring-loaded intermediate at every cross-linking point. A second, on-demand step to initiate fluorescence generation subsequently imparts the properties of the chemical transformation to the material itself. The synthesised particles are narrow-disperse with an average diameter ranging from 170-380 nm.
ABSTRACT
We introduce a protecting-group-free concept for the powerful para-fluoro-thiol reaction (PFTR) employing a source of fluoride ions as base. The reaction is shown to be self-propagating, with under-stoichiometric amounts of base, thus effectively foregoing the need for high base concentrations. Careful tuning of the solvent-thiol combination allows for quantitative conversion, in some cases within a short timeframe, when only minimal amounts of base are used, allowing the PFTR reaction to essentially proceed base-free.