Kyriakos C. Stylianou

A Guest-Responsive Fluorescent 3D Microporous Metal−Organic Framework Derived from a Long-Lifetime Pyrene Core

The carboxylate ligand 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy)-based on the strongly fluorescent long-lifetime pyrene core-affords a permanently microporous fluorescent metal-organic framework, [In(2)(OH)(2)(TBAPy)].(guests) (1), displaying 54% total accessible volume and excellent thermal stability. Fluorescence studies reveal that both 1 and TBAPy display strong emission bands at 471 and 529 nm, respectively, upon excitation at 390 nm, with framework coordination of the TBAPy ligands significantly increasing the emission lifetime from 0.089 to 0.110 ms. Upon desolvation, the emission band for the framework is shifted to lower energy: however, upon re-exposure to DMF the as-made material is regenerated with reversible fluorescence behavior. Together with the lifetime, the emission intensity is strongly enhanced by spatial separation of the optically active ligand molecules within the MOF structure and is found to be dependent on the amount and chemical nature of the guest species in the pores. The quantum yield of the material is found to be 6.7% and, coupled with the fluorescence lifetime on the millisecond time scale, begins to approach the values observed for Eu(III)-cryptate-derived commercial sensors.

An Adaptable Peptide-Based Porous Material

Swelling Pores Porosity is a key parameter when selecting materials for catalysts, chemical separations, gas storage, host-guest interactions, and related chemical processes. In most cases the porosity of a material is fixed. Rabone et al. (p. 1053; see the Perspective by Wright) have described a molecular material in which the size of the pores changed during the sorption process. The porosity increased because a dipeptide linker between metal centers reoriented during uptake of some gases, thus improving the capacity of the material to adsorb. Conformational changes in a porous material during the sorption of small molecules lead to a dynamic increase in porosity. Porous materials find widespread application in storage, separation, and catalytic technologies. We report a crystalline porous solid with adaptable porosity, in which a simple dipeptide linker is arranged in a regular array by coordination to metal centers. Experiments reinforced by molecular dynamics simulations showed that low-energy torsions and displacements of the peptides enabled the available pore volume to evolve smoothly from zero as the guest loading increased. The observed cooperative feedback in sorption isotherms resembled the response of proteins undergoing conformational selection, suggesting an energy landscape similar to that required for protein folding. The flexible peptide linker was shown to play the pivotal role in changing the pore conformation.

CO2 selectivity of a 1D microporous adenine-based metal–organic framework synthesised in water

The coordination of adenine to Ni(2+) forms a dimer unit which can be linked by 3,5-pyrazoledicarboxylic acid into chains which assemble under hydrothermal conditions via hydrogen bonding into a robust porous network. The material displays selectivity for CO(2) over CH(4) and an isosteric heat which increases with guest loading.

A Metal−Organic Framework with a Covalently Prefabricated Porous Organic Linker

We report here the synthesis of a metal-organic framework comprising an organic cage linker with covalently prefabricated, intrinsic porosity. The network can be compared to a porous rock salt structure where the pores are partially filled by charge-balancing cations.

Dimensionality transformation through paddlewheel reconfiguration in a flexible and porous Zn-based metal-organic framework.

The reaction between Zn and a pyrene-based ligand decorated with benzoate fragments (H(4)TBAPy) yields a 2D layered porous network with the metal coordination based on a paddlewheel motif. Upon desolvation, the structure undergoes a significant and reversible structural adjustment with a corresponding reduction in crystallinity. The combination of computationally assisted structure determination and experimental data analysis of the desolvated phase revealed a structural change in the metal coordination geometry from square-pyramidal to tetrahedral. Simulations of desolvation showed that the local distortion of the ligand geometry followed by the rotation and displacement of the pyrene core permits the breakup of the metal-paddlewheel motifs and the formation of 1D Zn-O chains that cross-link adjacent layers, resulting in a dimensionality change from the 2D layered structure to a 3D structure. Constrained Rietveld refinement of the powder X-ray diffraction pattern of the desolvated phase and the use of other analytical techniques such as porosity measurements, (13)C CP MAS NMR spectroscopy, and fluorescence spectroscopy strongly supported the observed structural transformation. The 3D network is stable up to 425 °C and is permanently porous to CO(2) with an apparent BET surface area of 523(8) m(2)/g (p/p° = 0.02-0.22). Because of the hydrophobic nature, size, and shape of the pores of the 3D framework, the adsorption behavior of the structure toward p-xylene and m-xylene was studied, and the results indicated that the shape of the isotherm and the kinetics of the adsorption process are determined mainly by the shape of the xylene isomers, with each xylene isomer interacting with the host framework in a different manner.

Enhanced Stability in Rigid Peptide‐Based Porous Materials

Pepped up: Notwithstanding the intrinsic conformational flexibility of peptides, [Zn(Gly-Thr)(2)] behaves as a robust porous metal-organic framework thanks to the rigidity introduced by the use of Gly-Thr (see scheme). This rigidity arises from the sequence of amino acids in the dipeptide that locks its conformational flexibility in the framework.

Shape Selectivity by Guest‐Driven Restructuring of a Porous Material

A flexible metal-organic framework selectively sorbs para- (pX) over meta-xylene (mX) by synergic restructuring around pX coupled with generation of unused void space upon mX loading. The nature of the structural change suggests more generally that flexible structures which are initially mismatched in terms of fit and capacity to the preferred guest are strong candidates for effective molecular separations.

Metal–Organic Frameworks: From Molecules/Metal Ions to Crystals to Superstructures

Metal-organic frameworks (MOFs) are among the most attractive porous materials known today, exhibiting very high surface areas, tuneable pore sizes and shapes, adjustable surface functionality, and flexible structures. Advances in the formation of MOF crystals, and in their subsequent assembly into more complex and/or composite superstructures, should expand the scope of these materials in many applications (e.g., drug delivery, chemical sensors, selective reactors and removal devices, etc.) and facilitate their integration onto surfaces and into devices. This Concept article aims to showcase recently developed synthetic strategies to control the one-, two- and three-dimensional (1-, 2- and 3D) organisation of MOF crystals.

Direct On‐Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature

We report herein an efficient, fast, and simple synthesis of an imine-based covalent organic framework (COF) at room temperature (hereafter, RT-COF-1). RT-COF-1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N2 and CO2 . The room-temperature synthesis has enabled us to fabricate and position low-cost micro- and submicropatterns of RT-COF-1 on several surfaces, including solid SiO2 substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink-jet printing.

Protecting metal-organic framework crystals from hydrolytic degradation by spray-dry encapsulating them into polystyrene microspheres

Many metal-organic frameworks are water labile, including the iconic Hong-Kong University of Science and Technology-1 (HKUST-1). Spray-dry encapsulation of HKUST-1 crystals into polystyrene microspheres is reported here to yield composites that are resistant to water but retain most of the excellent gas sorption capacity of HKUST-1. These composites are demonstrated to exhibit superior water adsorption/desorption cycling, maintaining the level of water uptake even after three cycles.