One-dimensional metal-organic framework photonic crystals used as platforms for vapor sorption.

We present the fabrication of one-dimensional photonic crystals (Bragg stacks) based on a microporous metal–organic framework material and mesoporous titanium dioxide. The Bragg stack heterostructures were obtained using two complementary synthesis approaches utilizing the bottom-up assembly of heterogeneous, i.e. two-component photonic crystal multilayer structures. Zeolitic imidazolate framework ZIF-8 and mesoporous titanium dioxide were chosen as functional components with different refractive indices. While ZIF-8 is intended to impart molecular selectivity, mesoporous TiO2 is used to ensure high refractive index contrast and to guarantee molecular diffusion within the Bragg stack. The combination of micro- and mesoporosity within one scaffold endows the 1D-MOF PC with characteristic adsorption properties upon exposure to various organic vapors. In this context, the sorption behavior of the photonic material was studied as a function of partial pressure of organic vapors. The results show that the multilayered photonic heterostructures are sensitive and selective towards a series of chemically similar solvent vapors. It is thus anticipated that the concept of multilayer heterogeneous photonic structures will provide a versatile platform for future selective, label-free optical sensors

Enhanced Synthesis of Metal-Organic Frameworks on the Surface of Electrospun Cellulose Nanofibers

This study reports the in situ crystal growth of HKUST-1 on electrospun cellulose nanofibers. Two different methods for introducing carboxyl groups on the nanofiber surface were used; HKUST-1 was then synthesized on the cellulose nanofiber surface using a layer-by-layer approach. The distribution of HKUST-1 on the nanofiber surface was highly dependent on the type of anionic pretreatment. The loading of HKUST-1 on the nanofiber surface could be controlled by the layer-by-layer synthesis and the BET surface area could be increased by a factor of 44 to 440 m2 g-1

Chelation-driven fluorescence deactivation in three alkali earth metal MOFs containing 2,2’-dihydroxybiphenyl-4,4’-dicarboxylate

First published online 04 Sep 2013Three new metal-organic frameworks (MOFs) have been synthesised from alkali earth metal ions of increasing ionic radii (Mg, Ca and Sr) and 2,2’-dihydroxybiphenyl-4,4’-dicarboxylic acid (H4diol). The distinct coordination environments, framework topologies and the non-coordinated diol moieties accessed are a result of using differently sized metal ions for MOF synthesis which affects the ability of the diol moieties to chelate the metal. Detailed structural analysis of [Sr3(H2diol)3(DMF)5], [Ca3.5(Hdiol)(H2diol)2(DMF)5] and [Mg(H2diol)(DMF)2] show distinctive variations in variable temperature expansion/contraction properties and porosity. In addition, [Sr3(H2diol)3(DMF)5] and [Ca3.5(Hdiol)(H2diol)2(DMF)5] display a broad fluorescence emission (λmax = ~435 nm) under ultraviolet light due to the presence of non-coordinated biphenyl-diol moieties within the structures, while chelation of Mg by the diol pocket in [Mg(H2diol)(DMF)2] leads to quenching of the ligand fluorescence.Damien Rankine, Tony D. Keene, Christopher J. Sumby and Christian J. Doona

Mechanistic insight into the sensing of nitroaromatic compounds by metal-organic frameworks

There has been extensive research on the sensing of explosive nitroaromatic compounds (NACs) using fluorescent metal-organic frameworks (MOFs). However, ambiguity in the sensing mechanism has hampered the development of efficient explosive sensors. Here we report the synthesis of a hydroxyl-functionalized MOF for rapid and efficient sensing of NACs and examine in detail its fluorescence quenching mechanisms. In chloroform, quenching takes place primarily by exciton migration to the ground-state complex formed between the MOF and the analytes. A combination of hydrogen-bonding interactions and ??????? stacking interactions are responsible for fluorescence quenching, and this observation is supported by single-crystal structures. In water, the quenching mechanism shifts toward resonance energy transfer and photo-induced electron transfer, after exciton migration as in chloroform. This study provides insight into florescence-quenching mechanisms for the selective sensing of NACs and reduces the ambiguity regarding the nature of interactions between the MOF and NACs

Chemical and structural stability of zirconium-based metal-organic frameworks with large three-dimensional pores by linker engineering

YesThe synthesis of metal–organic frameworks with large three-dimensional channels that are permanently porous and chemically stable offers new opportunities in areas such as catalysis and separation. Two linkers (L1=4,4′,4′′,4′′′-([1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(ethyne-2,1-diyl)) tetrabenzoic acid, L2=4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid) were used that have equivalent connectivity and dimensions but quite distinct torsional flexibility. With these, a solid solution material, [Zr6O4(OH)4(L1)2.6(L2)0.4]⋅(solvent)x, was formed that has three-dimensional crystalline permanent porosity with a surface area of over 4000 m2 g−1 that persists after immersion in water. These properties are not accessible for the isostructural phases made from the separate single linkers.Financial support from EPSRC under EP/H000925, access to the HPC service ARCHER via EP/L000202. S.N. thanks the EU for a Marie Curie fellowship (PIEF-GA-2010-274952). C.M.-G. thanks the Spanish MINECO for a Ramón y Cajal Fellowship (RYC-2012-10894)

Two consecutive magneto-structural gas-solid transformations in non-porous molecular materials

Modification of the magnetic properties in a solid-state material upon external stimulus has attracted much attention in the recent years for their potential applications as switches and sensors. Within the field of coordination polymers, gas sorption studies typically focus on porous solids, with the gas molecules accommodating in the channels. Here we present a 1D non-porous coordination polymer capable of incorporating HCl gas molecules, which not only causes a reordering of its atoms in the solid state but also provokes dramatic changes in the magnetic behaviour. Subsequently, a further solid-gas transformation can occur with the extrusion of HCl gas molecules causing a second structural rearrangement which is also accompanied by modification in the magnetic path between the metal centres. Unequivocal evidence of the two-step magnetostructural transformation is provided by X-ray single-crystal diffraction

Halochromic coordination polymers based on a triarylmethane dye for reversible detection of acids

Chromeazurol B (Na2HL) is a pH-sensitive (halochromic) dye based on a hydroxytriarylmethane core and two carboxylate functional groups, which makes it suitable for the synthesis of coordination polymers. Two new coordination polymers [NaZn4(H2O)3(L)3]·3THF·3H2O (1) and [Zn3(H2O)3(μ2- OH2)(μ3-OH)(HL)2(H2L)]·2THF·3H2O (2) incorporating Chromeazurol B linkers have been prepared and characterised. The structure of 1 comprises pentanuclear heterometallic {Zn4Na} nodes linked by six L3– anions to give a layered structure with a honeycomb topology. 2 crystallizes as a double-chain ribbon (ladder) structure with two types of metal node: a mononuclear Zn(II) cation and tetranuclear {Zn(II)}4 cluster. Chromeazurol B anions link each tetranuclear cluster to four individual Zn(II) cations and each Zn(II) cation with four tetranuclear clusters. Both compounds show pH-sensitivity in water solution which can be observed visually, giving the first example of a halochromic coordination polymer. The halochromic properties of 1 towards HCl vapors were systematically investigated. As-synthesized violet-grey 1 reversibly changes color from orange to pink in the presence of vapors of 2M and 7M HCl, respectively. The coordination of the Chromeazurol B anion at each color stage was examined by diffuse reflectance spectroscopy and FT-IR measurements. The remarkable stability of 1 to acid and the observed reversible and reproducible color changes provide a new design for multifunctional sensor materials