Twining Poly(polyoxometalate) Chains into Nanoropes.

Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)-a polynorbornene backbone with inorganic polyoxometalate cluster pendants-upon addition of a non-solvent to its dilute solution is reported. A three-dimensional network of tangled and snake-like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non-solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application.

Incorporation of Polyoxometalates into Polymers to Create Linear Poly(polyoxometalate)s with Catalytic Function.

Organic polymers have been found widespread commercial applications due to their easy processing and attractive mechanical properties. Concurrently, inorganic polyoxometalates (POMs), a class of metal-oxygen anionic and nanosized clusters of early transition metals, have a wide range of attractive functions and are used in industrial catalysis. In this communication, we report a new approach to creating the first linear poly(polyoxometalate)s that combine the advantages of polymers and POM clusters. In the experiment, a POM-containing norbornene monomer was first synthesized by linking a Wells-Dawson-type POM with a norbornene derivative. The monomer was polymerized in the presence of a Grubbs catalyst under mild conditions with yields nearly 100% in a living and controllable manner. The resulting poly(polyoxometalate)s have controllable molecular weights and a well-defined hybrid structure of an organic polynorbornene backbone with large pendant groups of the nanosized POM clusters. Thus, they form good films and have a good catalytic performance. Our findings not only pave the way for incorporating the POM clusters into polymers with well-defined structures and high molecular weights, but also offer a competitive strategy for developing more novel catalytic systems by introducing the poly(polyoxometalate)s.

Langmuir and Langmuir-Blodgett films of hybrid amphiphiles with a polyoxometalate headgroup.

A hybrid was at first synthesized by a postfunctionalization of an aminomethane trisalkoxo-functionalized Anderson-type polyoxometalate (POM) encapsulated by three tetrabutylammonium ions using a 3,5-bis(tetradecyloxy)benzoic acid by amidation. Then the three TBA(+) counter cations were programmatically replaced by protons (H(+)) following a molecule-to-amphiphile conversion. In this way one hybrid and three POM-containing hybrid amphiphiles (PCHAs) were acquired by adjusting the number (n) of TBA(+) ions and number (3 - n) of H(+) ions (n = 3, 2, 1, and 0). These compounds can be spread onto a water surface to form a Langmuir monolayer film at the air-water interface. Surface pressure-molecular area measurements exhibit the TBA(+) (H(+)) number playing an important role in the forming ability and stability of Langmuir monolayer films. Also, the Langmuir-Blodgett (LB) technique has been used to transfer the monolayer film onto solid supports to fabricate solid multilayer films. It was found that the PCHA with three H(+) ions had the best Langmuir film-forming ability and thus formed stable LB films with a two-dimensional ordered structure. Our findings are instructive in fabricating and using solid films of the amphiphiles with POM headgroups.

1-Methyl-5-phen-oxy-3-trifluoro-methyl-1H-pyrazole-4-carbaldehyde oxime.

In the title compound, C(12)H(10)F(3)N(3)O(2), the dihedral angle between the phenyl and pyrazole rings is 96.6 (3)°. In the crystal, pairs of O-H⋯N hydrogen bonds link the mol-ecules, forming inversion dimers. Weak inter-molecular C-H⋯F hydrogen bonds are also observed.