Photoswitching of Co(ii)-based coordination cages containing azobenzene backbones.

Inclusion of photoswitchable azobenzene units as spacers into ditopic bridging ligands Lm and Lp, containing two chelating pyrazolyl-pyridine termini, allows formation of metal complex assemblies with Co(ii) that undergo a range of light-induced structural transformations. One notable result is the light-induced conversion of a Co2(Lp)3 dinuclear triple helicate (based on the E ligand isomer) to a C 3-symmetric Co4(Lp)6 assembly, assumed to be an edge-bridged tetrahedral cage, based on the Z ligand isomer. Another is the preparation of a series of Co4(Lm)6 complexes, of which Co4(E-Lm)6 was crystallographically characterised and consists of a pair of Co2(Lm)2 double helicates connected by an additional two bridging ligands which span the pair of helicate units, giving a cyclic Co4 array in which one and then two bridging ligands alternate around the periphery. A set of Co4(Lm)6 complexes could be prepared containing different ratios of Z : E ligand isomers (0 : 6, 2 : 4, 4 : 2 and 6 : 0) of which Co4(Z-Lm)2(E-Lm)4 was particularly stable and dominated the speciation behaviour, either during light-induced switching of the ligand geometry in pre-formed complexes, or when ligand isomers were combined in different proportions during the preparation. These examples of (i) interconversion between Co2L3 (helicate) and (ii) Co4L6 (cage) assemblies with Lp, and the interconversion between a series of Co4L6 assemblies Co4(Z-Lm)n(E-Lm)6-n with Lm, constitute significant advances in the field of photoswitchable supramolecular assemblies.

The preservation of sarin and O,O'-diisopropyl fluorophosphate inside coordination cage hosts.

The host-guest chemistry of O,O'-diisopropyl fluorophosphate (DFP), a phosphonofluoridate G-series chemical warfare agent simulant, was investigated in the presence of a number of octanuclear cubic coordination cage hosts. The aim was to demonstrate cage-catalysed hydrolysis of DFP at near neutral pH: however, two octanuclear coordination cages, HPEG (containing water-solubilising PEG groups) and HW (containing water-solubilising hydroxymethyl groups), were actually found to increase the lifetime of DFP in aqueous buffer solution (pH 8.7). Crystallographic analysis of DFP with a structurally related host cage revealed that DFP binds to windows in the cage surface, not in the internal cavity. The phosphorus-fluorine bond is directed into the cavity rather than towards the external environment, with the cage/DFP association protecting DFP from hydrolysis. Initial studies with the chemical warfare agent (CWA) sarin (GB) with HPEG cage in a buffered solution also showed a drastically reduced rate of hydrolysis for sarin when bound in the host cage. The ability of these cages to inhibit hydrolysis of these P-F bond containing organophosphorus guests, by encapsulation, may have applications in forensic sample preservation and analysis.

Interaction of anions with the surface of a coordination cage in aqueous solution probed by their effect on a cage-catalysed Kemp elimination.

An octanuclear M8L12 coordination cage catalyses the Kemp elimination reaction of 5-nitro-1,2-benzisoxazole (NBI) with hydroxide to give 2-cyano-4-nitrophenolate (CNP) as the product. In contrast to the previously-reported very efficient catalysis of the Kemp elimination reaction of unsubstituted benzisoxazole, which involves the substrate binding inside the cage cavity, the catalysed reaction of NBI with hydroxide is slower and occurs at the external surface of the cage, even though NBI can bind inside the cage cavity. The rate of the catalysed reaction is sensitive to the presence of added anions, which bind to the 16+ cage surface, displacing the hydroxide ions from around the cage which are essential reaction partners in the Kemp elimination. Thus we can observe different binding affinities of anions to the surface of the cationic cage in aqueous solution by the extent to which they displace hydroxide and thereby inhibit the catalysed Kemp elimination and slow down the appearance of CNP. For anions with a -1 charge the observed affinity order for binding to the cage surface is consistent with their ease of desolvation and their ordering in the Hofmeister series. With anions that are significantly basic (fluoride, hydrogen carbonate, carboxylates) the accumulation of the anion around the cage surface accelerates the Kemp elimination compared to the background reaction with hydroxide, which we ascribe to the ability of these anions to participate directly in the Kemp elimination. This work provides valuable mechanistic insights into the role of the cage in co-locating the substrate and the anionic reaction partners in a cage-catalysed reaction.