Photophysics of cage/guest assemblies : photoinduced electron transfer between a coordination cage containing osmium(II) luminophores, and electron-deficient bound guests in the central cavity

An octanuclear cubic Os4Zn4 coordination cage, containing Os(II) tris-diimine units at four of the eight vertices which are good photoelectron donors from their 3MLCT excited state, performs photoinduced electron transfer to electron-accepting organic guests which bind in the central cavity in water via the hydrophobic effect: the resulting charge-separated states have lifetimes of ca. 200 ps and have been characterized by transient absorption spectroscopy

Dispersible microporous di-block co-polymer Nanoparticles via polymerisation-induced self-assembly

Microporous materials are predominantly formed as insoluble powders which means that they can be difficult to process. Here we report a new class of solvent-dispersible porous polymers synthesised by reversible addition-fragmentation chain transfer mediated polymerisation-induced self-assembly (RAFT-mediated PISA), formed from a PEG macro-CTA polymerised with divinylbenzene and fumaronitrile. The particles have a dual morphology consisting of smaller spheres of 24-29 nm aggregated into larger particles of 204 - 262 nm. Gas sorption analysis showed the particles to have BET surface areas of 274 to 409 m2/g with internal pore sizes centred around 1.8 nm and further larger pores arising from the sphere packing of the aggregates. The particles were found to be photoluminescent (emission λmax = 326 nm) when exposed to UV light which could be quenched by the addition of nitroaromatic compounds. For example, 99% if the emission was quenched in the presence of 38 ppm of picric acid