Towards a self-assembled honeycomb structure via diaminotriptycene metal complexes.

We illustrate a new approach toward the synthesis of a porous supramolecular honeycomb based on triptycene. A coordination polymer has been prepared where the triptycene groups are linked through triptycenesemiquinonediimine platinum complexes, but the product is disordered rather than the intended honeycomb structure. A model platinum complex and its (15)N-labeled isotopomer have been prepared and characterized.

Applications of functionalized and nanoparticle-modified nanocrystalline cellulose.

Nanocrystalline cellulose (NCC), a rod-shaped nanoscale material with exceptional strength and physicochemical properties, can be prepared from inexpensive renewable biomass. Besides its potential use as a reinforcing agent for industrial biocomposites, pristine NCC exhibits low toxicity and poses no serious environmental concerns, providing impetus for its use in bioapplications. Here, we review recent developments in the use of modified NCC for emerging bioapplications, specifically enzyme immobilization, antimicrobial and medical materials, green catalysis, biosensing and controlled drug delivery. We focus on the modification of NCC with chemical functionalities and inorganic nanoparticles, reviewing practical considerations such as reusability, toxicity and scale-up capability.

Catalysis using gold nanoparticles decorated on nanocrystalline cellulose.

A novel nanocomposite was prepared by deposition of carbonate-stabilized Au nanoparticles (AuNPs) onto the surface of poly(diallyldimethyl ammonium chloride) (PDDA)-coated carboxylated nanocrystalline cellulose (NCC). The hybrid material possessed AuNPs (1.45% by weight) with an average diameter of 2.95 ± 0.06 nm. The catalytic activity of AuNP/PDDA/NCC for reducing 4-nitrophenol to 4-aminophenol was compared to other Au-supported composites. An activation energy of 69.2 kJ mol(-1) was obtained for the reaction. Indeed, the reaction rate constant k of (5.1 ± 0.2) × 10(-3) s(-1) was comparable to the benchmark literature value obtained using AuNPs (<5 nm in diameter) decorated on a network of crystalline cellulose fibers. Our strategy promotes the use of natural resources to prepare reusable hybrid inorganic-organic materials for important reactions with facilitated product isolation/purification.

Synthesis of furfural from xylose by heterogeneous and reusable nafion catalysts.

Nafion 117 has been proven as a robust and reusable heterogeneous catalyst for the dehydration of 9.1 % (w/w) xylose in dimethyl sulfoxide (DMSO) to yield 60 % furfural in 2 h at 150 °C. The catalytic high activity promoted shorter reaction times to limit the formation of side-products which otherwise would lead to decreased yields. Within the allowable operating temperature range of Nafion (125 to 175 °C), the reaction was kinetically controlled. In corroboration with AFM and SEM imaging, ATR-FTIR confirmed that the Nafion catalytic activity remained unchanged after 15 repeated uses. With excellent chemical and thermal stability under the conditions for xylose dehydration compared to existing solid acid catalysts, this reusable Nafion system could be a step towards the more economical production of furfural from renewable biomass, an intermediate chemical for the preparation of value-added chemicals.

Bimetallic Schiff base complexes: models for conjugated shape-persistent metallopolymers.

New Schiff base ligands with two metal binding sites have been prepared. Copper and zinc complexes of the ligands, which serve as models for rigid, conjugated metallopolymers, were synthesized and characterized. The copper complexes display only weak intramolecular antiferromagnetic interactions, suggesting that the polymer structure is not useful for developing magnetic materials. Preliminary investigations of the novel polymers, including the preparation of a conjugated zinc-containing polymer, are reported.

Iptycenes in supramolecular and materials chemistry.

Iptycenes, including triptycene as the smallest member, are rigid molecules with shapes that lead them to form open structures with substantial "free volume". There is a great deal of excitement in the application of these molecules to supramolecular chemistry, where researchers have taken advantage of their unique properties to construct new molecules and materials, including molecular machines, novel liquid crystals, and porous polymers for chemical sensing. This tutorial review highlights the application of iptycenes to the supramolecular chemistry of crystal engineering, host-guest complexes, molecular machines, polymers, and liquid crystals.

Zinc carboxylate cluster formation in conjugated metallomacrocycles: evidence for templation.

A new [3 + 3] Schiff base macrocycle incorporating three N2O2 salphen-type binding sites and peripheral neopentyloxy substituents has been prepared. The incorporation of Zn2+ ions into this and related conjugated Schiff base macrocycles has been studied by NMR spectroscopy, mass spectrometry, and X-ray diffraction. When reacted with 7 equiv of zinc acetate, the macrocycles template the formation of heptanuclear complexes. Two tetranuclear Zn2+ complexes that are plausible intermediates in the assembly of the heptanuclear complexes have been isolated and structurally characterized. These reactive intermediates are promising substrates for the synthesis of polynuclear, mixed-metal clusters. We also demonstrate that this chemistry may be generalized to other bridging carboxylate ligands, such as methacrylate.

Synthesis and structural investigation of new triptycene-based ligands: en route to shape-persistent dendrimers and macrocycles with large free volume.

Triptycene was used to build a series of ligands containing pyrazine groups for use in forming coordination frameworks and as model compounds toward target shape-persistent dendrimers and macrocycles. The phenylenediamine precursors are formed by controlled double nitration/reduction of triptycene, followed by condensation with triptycenyl o-quinone to form the ligands. Solid-state structures show that the ligands favor packing in layered structures with intermolecular pi stacking. Increasing the length of the wings still allows for effective packing, but increasing the number of pyrazine groups or adding more triptycenyl moieties reduces packing efficiency. To demonstrate the potential of these molecules to function as ligands, a coordination complex of 15 with copper(I) iodide was obtained and found to form dimers that pack into a layered arrangement.

Heptametallic bowl-shaped complexes derived from conjugated Schiff-base macrocycles: synthesis, characterization, and X-ray crystal structures.

The reaction of chelating conjugated macrocycles 1a-c with Zn(OAc)2 gives bowl-shaped heptanuclear Zn complexes featuring Zn in tetrahedral, octahedral, and square-pyramidal geometries. Crystallographic and NMR results indicate that vacant Zn coordination sites within the bowl may be accessed, suggesting that these coordination complexes may be used as mimics for Zn fingers and carbonic anhydrase.

Scope and limitations of the base-catalyzed phospha-peterson P=C bond-forming reaction.

Phosphaalkenes (MesP=CRR': R = R' = Ph (1a); R = R' = 4-FC6H4 (1b); R = Ph, R' = 4-FC6H4 (1c); R = R' = 4-OMeC6H4 (1d); R = Ph, R' = 4-OMeC6H4 (1e); R = Ph, R' = 2-pyridyl (1f)) are prepared from the reaction of MesP(SiMe3)2 and O=CRR' in the presence of a trace of KOH or NaOH. The base-catalyzed phospha-Peterson reaction is quantitated by NMR spectroscopy, and isolated yields of phosphaalkene between 40 and 70% are obtained after vacuum distillation and/or recrystallization. The asymmetrically substituted phosphaalkenes (1c, 1e, 1f) form as 1:1 mixtures of E and Z isomers; however, X-ray crystallography reveals that the E isomers crystallize preferentially. Interestingly, E-1e and E-1f readily isomerize in solution in the dark, although the rate of isomerization is much faster when samples are exposed to light. X-ray crystal structures of 1b, E-1e, and E-1f reveal that the P=C bond lengths (average of 1.70 A) are in the long end of the range typically found in phosphaalkenes (1.61-1.71 A). Attempts to prepare isolable P-adamantyl phosphaalkenes following this route were unsuccessful. Although AdP=CPh2 (2a) is detected by 31P NMR spectroscopy, attempts to isolate this species afforded the 1,2-diphosphetane (AdPCPh2)2 (3a), which was characterized by X-ray crystallography.

Robust non-interpenetrating coordination frameworks from new shape-persistent building blocks.

New shape-persistent ligands derived from triptycene were synthesized, and reaction with copper iodide results in the assembly of non-interpenetrating coordination frameworks with hydrophobic void spaces. These structures are thermally stable and display reversible solvent adsorption, and 1H NMR experiments show that they can be used to remove benzene from water.

N-salicylideneanilines: tautomers for formation of hydrogen-bonded capsules, clefts, and chains.

[structure: see text] The synthesis, characterization, and solid-state structures of new salicylaldimines are reported. Bis(N-salicylideneaniline)s (BSANs) and tris(N-salicylideneaniline)s (TSANs) are sterically encumbered compounds featuring a central six-membered ring in the keto-enamine tautomer. When extended with additional functional groups, these molecules may form hydrogen-bonded capsules, clefts, and extended structures. A TSAN with N-(t)()BOC-o-phenylenediamine groups has been structurally investigated. The complementary hydrogen-bonding motif in this molecule leads it to form dimers in solution and in the solid state. A BSAN with N-(t)()BOC-o-phenylenediamine substituents forms a hydrogen-bonded cleft in solution but forms an extended hydrogen-bonded ladder assembly of cofacial dimers in the solid state. When N-(t)()BOC-1,8-naphthalenediamine was utilized to extend the cleft, an unusual perimidine structure was obtained with the central core in the enol tautomer. In addition, ab initio calculations have been used to support the assignment of the keto-enamine or enol-imine tautomers of the BSANs and TSANs and to predict tautomerization in related BSANs and TSANs.

Highly stable keto-enamine salicylideneanilines.

[reaction: see text] Highly stable NH salicylideneanilines have been prepared by reaction of 1,3,5-triformylphloroglucinol with aniline derivatives. The NH form was confirmed by X-ray crystallographic data, as well as by NMR studies. A convenient one-step synthesis of triformylphloroglucinol is also reported.