Correlation of Local Structure and Diffusion Pathways in the Modulated Anisotropic Oxide Ion Conductor CeNbO(4.25).

CeNbO4.25 is reported to exhibit fast oxygen ion diffusion at moderate temperatures, making this the prototype of a new class of ion conductor with applications in a range of energy generation and storage devices. To date, the mechanism by which this ion transport is achieved has remained obscure, in part due to the long-range commensurately modulated structural motif. Here we show that CeNbO4.25 forms with a unit cell ∼12 times larger than the stoichiometric tetragonal parent phase of CeNbO4 as a result of the helical ordering of Ce(3+) and Ce(4+) ions along z. Interstitial oxygen ion incorporation leads to a cooperative displacement of the surrounding oxygen species, creating interlayer "NbO6" connectivity by extending the oxygen coordination number to 7 and 8. Molecular dynamic simulations suggest that fast ion migration occurs predominantly within the xz plane. It is concluded that the oxide ion diffuses anisotropically, with the major migration mechanism being intralayer; however, when obstructed, oxygen can readily move to an adjacent layer along y via alternate lower energy barrier pathways.

Multiphoton harvesting metal-organic frameworks.

Multiphoton upconversion is a process where two or more photons are absorbed simultaneously to excite an electron to an excited state and, subsequently, the relaxation of electron gives rise to the emission of a photon with frequency greater than those of the absorbed photons. Materials possessing such property attracted attention due to applications in biological imaging, photodynamic therapy, three-dimensional optical data storage, frequency-upconverted lasing and optical power limiting. Here we report four-photon upconversion in metal-organic frameworks containing the ligand, trans, trans-9,10-bis(4-pyridylethenyl)anthracene. The ligand has a symmetrical acceptor-π-donor-π-acceptor structure and a singlet biradical electronic ground state, which boosted its multiphoton absorption cross-sections. We demonstrate that the upconversion efficiency can be enhanced by Förster resonance energy transfer within host-guest metal-organic frameworks consisting of encapsulated high quantum yielding guest molecules. Using these strategies, metal-organic framework materials, which can exhibit frequency-upconverted photoluminescence excited by simultaneous multiphoton absorption, can be rationally designed and synthesized.

Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state.

Solid-state [2+2] photochemical cycloaddition reactions have been extensively studied after the classical work of Schmidt in the 1960s. Of these, trans-1,2-bis(4'-pyridyl)ethylene (bpe) is one of the well-studied alkenes to synthesize tetrakis(4-pyridyl)cyclobutane (tpcb). However, almost all the solid-state [2+2] cycloaddition reactions of bpe yielded, almost exclusively, one of the four possible isomers, namely, the rctt-tpcb (r=regio c=cis and t=trans). Here we describe a stereoselective synthesis of the tetrahedrally disposed rtct-tpcb by the solid-state thermal isomerization of the rctt-isomer in atmospheric air. We propose that this isomerization occurs through a topochemical unimolecular mechanism by a radical chain pathway, initiated by molecular oxygen. This is supported by the nature of products formed in air and nitrogen, detection of a radical in ESR spectral studies, ESI-MS crossover experiments, VT PXRD studies along with QM, MD and docking calculations. The formation of a unique isomer by thermal isomerization may be a general phenomenon to quantitatively synthesize other useful stereoisomers from the existing isomers of cyclobutane derivatives.

Pseudomorphic 2A--> 2M--> 2H phase transitions in lanthanum strontium germanate electrolyte apatites.

Apatite-like materials are of considerable interest as potential solid oxide fuel cell electrolytes, although their structural vagaries continue to attract significant discussion. Understanding these features is crucial both to explain the oxide ion conduction process and to optimise it. As the composition of putative P6(3)/m apatites with ideal formula [A(I)(4)][A(II)(6)][(BO(4))(6)][X](2) is varied the [A(I)(4)(BO(4))(6)] framework will flex to better accommodate the [A(II)(6)X(2)] tunnel component through adjustment of the A(I)O(6) metaprism twist angle (varphi). The space group theory prescribes that framework adaptation during phase changes must lead to one of the maximal non-isomorphic subgroups of P6(3)/m (P2(1), P2(1)/m, P1[combining macron]). These adaptations correlate with oxygen ion conduction, and become crucial especially when the tunnels are filled by relatively small ions and/or partially occupied, and if interstitial oxygens are located in the framework. Detecting and completely describing these lower symmetry structures can be challenging, as it is difficult to precisely control apatite stoichiometry and small departures from the hexagonal metric may be near the limits of detection. Using a combination of diffraction and spectroscopic techniques it is shown that lanthanum strontium germanate oxide electrolytes crystallise as triclinic (A), monoclinic (M) and hexagonal (H) bi-layer pseudomorphs with the composition ranges: [La(10-x)Sr(x)][(GeO(4))(5+x/2)(GeO(5))(1-x/2)][O(2)] (0