A [4+2] Condensation Strategy to Imine-Linked Single-Crystalline Zeolite-Like Zinc Phosphate Frameworks.

Double-4-ring zinc phosphate (D4R), [Zn(dipp)(4-Py-CHO)]4 (2) (dipp=diiminopyridine), bearing four formyl groups, has been utilized as a building block (SBU) for the synthesis of a new class of imine-linked [4+2] COF-like polycrystalline zinc phosphate frameworks. Reactions of 2 with a series of linear aromatic diamines results in the formation of polycrystalline frameworks [Zn4 (dipp)4 (L)2 ]n (3-6) (L=L1 to L4 , diimines formed by condensation of 4-pyridine carboxaldehyde with diamines). Employing an alternative synthetic strategy, through a diffusion-controlled slow reaction of 2 with the pre-synthesized 4,4'-bispyridyl bisimine (L3 ), [Zn4 (dipp)4 (L3 )2 ]n (5') has been obtained as single crystals. Complex 5' is a 3D-framework, exhibiting a rare eightfold interpenetrated diamondoid network. The long spacer length (19.6 Å) results in extensive entanglement in 5'. Powder diffraction data suggest that these compounds are isoreticular 3D-frameworks. To study the effect of the relative position of pyridyl donors with respect to the central benzidine moiety, 3,3'-bispyridyl bisimine (L5 ) was investigated as the spacer. A slow reaction of 1 b with L5 leads to the isolation of a 2D-boxed-sheet coordination polymer [Zn4 (dipp)4 (L5 )2 ]n (7). Selective formation of 3D-framework 5' from L3 and the 2D-framework 7 from L5 is due to the angles created by the coordination of para- and meta-pyridyl nitrogen centers at the zinc centers of the D4R cubane. Compound 5' has been utilized as a catalyst for Knoevenagel condensation.

Tuning the electronic energy level of covalent organic frameworks for crafting high-rate Na-ion battery anode.

Crystalline Covalent Organic Frameworks (COFs) possess ordered accessible nano-channels. When these channels are decorated with redox-active functional groups, they can serve as the anode in metal ion batteries (LIB and SIB). Though sodium's superior relative abundance makes it a better choice over lithium, the energetically unfavourable intercalation of the larger sodium ion makes it incompatible with the commercial graphite anodes used in Li-ion batteries. Also, their sluggish movement inside the electrodes restricts the fast sodiation of SIB. Creating an electronic driving force at the electrodes via chemical manipulation can be a versatile approach to overcome this issue. Herein, we present anodes for SIB drawn on three isostructural COFs with nearly the same Highest Occupied Molecular Orbitals (HOMO) levels but with varying Lowest Unoccupied Molecular Orbitals (LUMO) energy levels. This variation in the LUMO levels has been deliberately obtained by the inclusion of electron-deficient centers (phenyl vs. tetrazine vs. bispyridine-tetrazine) substituents into the modules that make up the COF. With the reduction in the cell-potential, the electrons accumulate in the anti-bonding LUMO. Now, these electron-dosed LUMO levels become efficient anodes for attracting the otherwise sluggish sodium ions from the electrolyte. Also, the intrinsic porosity of the COF favors the lodging and diffusion of the Na+ ions. Cells made with these COFs achieve a high specific capacity (energy density) and rate performance (rapid charging-discharging), something that is not as easy for Na+ compared to the much smaller sized Li+. The bispyridine-tetrazine COF with the lowest LUMO energy shows a specific capacity of 340 mA h g-1 at 1 A g-1 and 128 mA h g-1 at a high current density of 15 A g-1. Only a 24% drop appears on increasing the current density from 0.1 to 1 A g-1, which is the lowest among all the top-performing COF derived Na-ion battery anodes.

1,3,5-Triphenylbenzene: a versatile photoluminescent chemo-sensor platform and supramolecular building block.

Fluorescence chemo-sensors for species of environmental and biological significance have emerged as a major research area in recent years. In this account, we describe fluorescence quenching as well as enhancement-based chemo-sensors obtained by employing C 3-symmetric 1,3,5-triphenylbenzene (1,3,5-TPB) as the fluorescence signalling unit. 1,3,5-TPB is a thermally and photochemically stable fluorescent platform with π-electron-rich characteristics. Starting from this platform, supramolecular, discrete, triphenylbenzene-carbazole, covalent-organic framework, covalent-organic polymer and conjugated polymer based sensors have been developed for the selective detection of polynitroaromatic compounds, trinitrotoluene (TNT), dinitrotoluene (DNT) and picric acid (PA). Tris-salicylaldimine Schiff bases have been synthesized for the selective sensing of fluoride ions through a fluorescence turn-on mechanism. It is likely that it should be possible to develop other highly selective and sensitive chemo-sensors by incorporating 1,3,5-TPB as the fluorophore unit.

Bulky Isopropyl Group Loaded Tetraaryl Pyrene Based Azo-Linked Covalent Organic Polymer for Nitroaromatics Sensing and CO2 Adsorption.

An azo-linked covalent organic polymer, Py-azo-COP, was synthesized by employing a highly blue-fluorescent pyrene derivative that is multiply substituted with bulky isopropyl groups. Py-azo-COP was investigated for its sensing and gas adsorption properties. Py-azo-COP shows selective sensing toward the electron-deficient polynitroaromatic compound picric acid among the many other competing analogs that were investigated. Apart from its chemosensing ability, Py-azo-COP (surface area 700 m2 g-1) exhibits moderate selectivity toward adsorption of CO2 and stores up to 8.5 wt % of CO2 at 1 bar and 18.2 wt % at 15.5 bar at 273 K, although this is limited due to the electron-rich -N=N- linkages being flanked by isopropyl groups. Furthermore, the presence of a large number of isopropyl groups imparts hydrophobicity to Py-azo-COP, as confirmed by the increased adsorption of toluene compared to that of water in the pores of the COP.

Catalysis and CO2 Capture by Palladium-Incorporated Covalent Organic Frameworks.

Triazine-based imine and ß-ketoenamine linked covalent organic frameworks (COFs), TAT-DHBD (1) and TAT-TFP (2), have been synthesized from 1,3,5-tris-(4'-aminophenyl)triazine (TAT) and 2,5-dihydroxybenzene-1,4-dicarboxaldehyde (DHBD) or 1,3,5-triformylphloroglucinol (TFP) under solvothermal conditions in dioxane/mesitylene mixture. These COFs exhibit significant surface areas owing to their meso- and micropores. The presence of basic nitrogen sites offers excellent affinity towards Pd nanoparticles and carbon dioxide. Post treatment of COFs 1 and 2 with palladium acetate gives PdII /TAT-DHBD (3) and PdII /TAT-TFP (4), which on reduction by NaBH4 yields Pd0 /TAT-DHBD (5) and Pd0 /TAT-TFP (6), respectively. The new COFs have been characterized by FTIR, solid-state 13 C NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), SEM, TEM, and Brunauer-Emmett-Teller (BET) surface area measurements. TEM studies corroborated the uniform distribution of PdII and Pd0 sites in the COFs. Compounds 3-6 are active towards the Suzuki-Miyaura cross-coupling of arenes with meager catalyst leaching even after five cycles. In addition, 4 exhibits CO2 uptake of 11 wt % and 7.5 wt % at 273 and 298 K, respectively, at 1 bar.