We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH(2) (UiO-66-NH(2)), Zr-bpdc (UiO-67), and Zr-tpdc-NH(2) (UiO-68-NH(2)) (H(2) bdc: terephthalic acid, H(2) bpdc: biphenyl-4,4'-dicarboxylic acid, H(2) tpdc: terphenyl-4,4''-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH(2) . Zr-tpdc-NH(2), a material with a structure analogous to that of Zr-bdc and Zr-bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1''-terphenyl-4,4''-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.

Emergent phenomena, including superconductivity and magnetism, found in the two-dimensional electron liquid (2-DEL) at the interface between the insulators lanthanum aluminate (LaAlO 3 ) and strontium titanate (SrTiO 3 ) distinguish this rich system from conventional 2D electron gases at compound semiconductor interfaces. The origin of this 2-DEL, however, is highly debated, with focus on the role of defects in the SrTiO 3 , while the LaAlO 3 has been assumed perfect. Here we demonstrate, through experiments and firstprinciple calculations, that the cation stoichiometry of the nominal LaAlO 3 layer is key to 2-DEL formation: only Al-rich LaAlO 3 results in a 2-DEL. Although extrinsic defects, including oxygen deficiency, are known to render LaAlO 3 /SrTiO 3 samples conducting, our results show that in the absence of such extrinsic defects an interface 2-DEL can form. Its origin is consistent with an intrinsic electronic reconstruction occurring to counteract a polarization catastrophe. This work provides insight for identifying other interfaces where emergent behaviours await discovery.

We present the synthesis and characterization of porous interpenetrated zirconium-organic frameworks (PIZOFs), a new family of metal-organic frameworks obtained from ZrCl(4) and the rodlike dicarboxylic acids HO(2)C[PE-P(R(1),R(2))-EP]CO(2) H that consist of alternating phenylene (P) and ethynylene (E) units. The substituents R(1),R(2) were broadly varied (alkyl, O-alkyl, oligo(ethylene glycol)), including postsynthetically addressable substituents (amino, alkyne, furan). The PIZOF structure is highly tolerant towards the variation of R(1) and R(2). This together with the modular synthesis of the diacids offers a facile tuning of the chemical environment within the pores. The PIZOF structure was solved from single-crystal X-ray diffraction analysis. The PIZOFs are stable under ambient conditions. PIZOF-2, the PIZOF prepared from HO(2)C[PE-P(OMe,OMe)-EP]CO(2)H, served as a prototype to determine thermal stability and porosity. It is stable up to 325 °C in air as determined by using thermogravimetry and powder X-ray diffraction. Argon sorption isotherms on PIZOF-2 revealed a Brunauer-Emmett-Teller (BET) surface area of 1250 m(2) g(-1) and a total pore volume of 0.68 cm(3) g(-1).

Context. Cold dust grains are responsible for the far-infrared and submillimetre (FIR/submm) emission observed by Herschel and Planck. Their thermal emission is usually expressed as a modified black body law in which the FIR/submm dust opacity, or mass absorption coefficient (MAC), is described by the MAC at a given wavelength κ λ 0 and the temperature-and wavelength-independent emissivity spectral index β. However, numerous data from previous space and balloon-borne missions and recently from Herschel and Planck show that the dust emission is not well understood, as revealed for example by the observed anti-correlation of β with the grain temperature. Aims. The aim of this work is to measure the optical properties of interstellar dust analogues at low temperatures to give astronomers the necessary data for interpreting FIR/submm observations such as those from the Herschel and Planck satellites. Methods. We synthesised, via sol-gel methods, analogues of interstellar amorphous silicate grains, rich in Mg and Ca, and having stoichiometry of olivine and pyroxene. The samples are characterised by various techniques to determine their composition, size, amorphisation degree. All the amorphous samples are annealed at 1100• C to study the crystallised materials for comparison. We measured the MAC of all the samples in the 2-25 μm range at room temperature and in the 100-1000/1500 μm range for grain temperatures varying from 300 to 10 K. Results. The experimental results show that, for all the amorphous samples, the grain MAC decreases when the grain temperature decreases and that the local spectral index, β, defined as the slope of the MAC curve, is anti-correlated with the grain temperature. These variations, which are not observed in the crystallised samples, are related to the amorphous nature of the samples. In addition, the spectral shape of the MAC is complex and cannot be described by a single spectral index over the 100-1500 μm range. At short wavelengths (λ ≤ 500/700 μm), β is in the range 1.6-2.1 for all grain temperature and grain composition. However, at longer wavelengths (λ ≥ 500/700 μm), β ≤ 2 for samples with a pyroxene stoichiometry and β ≥ 2 for samples with an olivine stoichiometry. Conclusions. The dust properties in the FIR/submm domain and at low temperature are more complicated than expected. The simplifying asymptotic expression based on a single temperature-and wavelength-independent spectral index used by astronomers is not appropriate to describe the dust MAC, hence the dust emission, and may induce significant errors on the derived parameters, such as the dust mass and the dust physical and chemical properties. Instead, dust emission models should use the dust MAC as a function of wavelength and temperature.