Kathleen V. Kilway

Control of functional group proximity and direction by conformational networks: synthesis and stereodynamics of persubstituted arenes

Abstract The cooperative nonbonded interactions present in hexaethylbenzene result in an arrangement of alkyl groups such that the 1,3,5 and 2,4,6 substituents point to opposite faces of the benzene ring. Correspondingly, derivatives of hexaethylbenzene have their functional groups convergent ( meta as in 1,3,5-trisubstituted-2,4,6-triethylbenzene) or divergent ( ortho , para as in 1,2-disubstituted-3,4,5,6-tetraethylbenzenes or 1,4-disubstituted-2,3,5,6-tetraethylbenzenes) due to this cooperative conformational network. To illustrate this structural feature and probe its dynamics, 1,4-di-X-2,3,5,6-tetraethylbenzenes have been synthesized. The dynamic stereochemistry of the disubstituted compounds has been studied by variable temperature 1 H NMR spectroscopy. Using the same strategy, the 1,3,5-tris(CH 2 Y)-2,4,6-triethylbenzenes have also been prepared. The steric bulk of the substituent in the disubstituted compounds has been found to influence the barrier height. The trends found are applicable for the use of these compounds as angular building blocks for the design of ligands, polymers, and supramolecular architectures.

Synthesis and structure of a twisted, colossal quinone

Abstract A very large quinone was prepared by the double Diels–Alder reaction of 2,5,9,12-tetra( t -butyl)diacenaphtho[1,2- b :1′,2′- d ]thiophene and benzoquinone. The crystal structure of the polycyclic product shows that the central anthraquinone ring system is quite twisted (50°), and the overall structure possesses approximate D 2 symmetry.

Unusually high SCLC hole mobility in solution-processed thin films of a polycyclic thiophene-based small-molecule semiconductor

SCLC hole mobilities up to 8.72 × 10−2 cm2 V−1 s−1, amongst the highest reported hole mobility values for solution-processed small-molecule organic semiconductors, are obtained from thermally annealed device-sized thin films of a thiophene-containing polycyclic aromatic hydrocarbon.

Molecular assembly of 1,3,5-tris(cyanomethyl) and 1,4-bis(cyanomethyl)arenes with silver triflate

Dicyano- and tricyano-substituted aromatic angular building blocks were systematically complexed with silver triflate, and their structures were determined by means of single-crystal X-ray diffraction. The molecular assembly of 1,3,5-tris(cyanomethyl)-2,4,6-triethylbenzene with silver triflate from benzene resulted in a layered structure with distorted square pyramidal silver sites. The structure resulting from the complexation of 1,3,5-tris(cyanomethyl)-2,4,6-trimethylbenzene with silver triflate is dependent on the solvent of crystallization. From benzene or toluene, reaction of 1,3,5-tris(cyanomethyl)-2,4,6-trimethylbenzene with silver triflate yielded a porous, channel-containing, solvated structure, but from acetone the resulting material was a network solid containing no solvent. Complexation of 1,4-bis(cyanomethyl)-2,3,5,6-tetraethylbenzene and 1,4-bis(cyanomethyl)-2,3,5,6-tetramethylbenzene with silver triflate resulted in network solids where the triflate anions were strongly coordinated to the silver.

Silorane resin supports proliferation, differentiation, and mineralization of MLO-A5 bone cells in vitro and bone formation in vivo†

Methyl methacrylate used in bone cements has drawbacks of toxicity, high exotherm, and considerable shrinkage. A new resin, based on silorane/oxirane chemistry, has been shown to have little toxicity, low exotherm, and low shrinkage. We hypothesized that silorane-based resins may also be useful as components of bone cements as well as other bone applications and began testing on bone cell function in vitro and in vivo. MLO-A5, late osteoblast cells, were exposed to polymerized silorane (SilMix) resin (and a standard polymerized bisGMA/TEGDMA methacrylate (BT) resin and compared to culture wells without resins as control. A significant cytotoxic effect was observed with the BT resin resulting in no cell growth, whereas in contrast, SilMix resin had no toxic effects on MLO-A5 cell proliferation, differentiation, nor mineralization. The cells cultured with SilMix produced increasing amounts of alkaline phosphatase (1.8-fold) compared to control cultures. Compared to control cultures, an actual enhancement of mineralization was observed in the silorane resin-containing cultures at days 10 and 11 as determined by von Kossa (1.8-2.0 fold increase) and Alizarin red staining (1.8-fold increase). A normal bone calcium/phosphate atomic ratio was observed by elemental analysis along with normal collagen formation. When used in vivo to stabilize osteotomies, no inflammatory response was observed, and the bone continued to heal. In conclusion, the silorane resin, SilMix, was shown to not only be non cytototoxic, but actually supported bone cell function. Therefore, this resin has significant potential for the development of a nontoxic bone cement or bone stabilizer.

Processing of yttrium aluminosilicate (YAS) glasses for dental composites

Two series of silicate glasses were processed to micron-size, sub-micron size, and nanoparticles using three different milling systems: ball milling, attrition, and high-energy milling. The effect of milling time and media size on particle size and contamination were investigated in aqueous and isopropanol suspensions. The particle size was determined using a laser-diffraction particle size analyzer and scanning electron microscopy. The smallest glass particles with a median particle size of 0.3 µm were achieved by a two-step comminution process in a high energy mill.

A Superior Synthesis of Longitudinally Twisted Acenes

Seven longitudinally twisted acenes (an anthracene, two tetracenes, three pentacenes, and a hexacene) have been synthesized by the addition of aryllithium reagents to the appropriate quinone precursors, followed by SnCl2 -mediated reduction of their diol intermediates, and several of these acenes have been crystallographically characterized. The new syntheses of the three previously reported twisted acenes, decaphenylanthracene (1), 9,10,11,20,21,22-hexaphenyltetrabenzo[a,c,l,n]pentacene (2), and 9,10,11,12,13,14,15,16-octaphenyldibenzo[a,c]tetracene (14), resulted in a reduction of the number of synthetic steps. As a consequence their overall yields were increased by factors of 50-, 24-, and 66-fold, respectively. All of the twisted acene syntheses reported here are suitable for the synthesis of at least gram quantities of these remarkable hydrocarbon materials.

Dynamic behavior of hydrogen bonding in hydrogen 5,6-acenaphthenedicarboxylate

Abstract The dynamic hydrogen bond behavior of hydrogen 5,6-acenaphthenedicarboxylate has been studied using NMR spectroscopy at variable concentration and temperature. From the concentration experiments, it is clear that there is an equilibrium between monomeric (intramolecularly hydrogen bonded) and aggregated (intermolecularly hydrogen bonded) species at room temperature. Upon cooling, the equilibrium shifts completely toward intramolecular hydrogen bonding, thereby overcoming the steric cost required to form the necessary eight-membered ring. This compound is one of the few examples which exhibits such behavior, and the first within the series of hydrogen dicarboxylates where it has been observed by NMR spectroscopy.

Synthesis and Structure of a Longitudinally Twisted Hexacene

The addition of phenyllithium to a polycyclic quinone, 9,11,12,21,22,24-hexaphenyltetrabenzo[a,c,n,p]hexacene-10,23-dione (10), followed by SnCl2 -mediated reduction of the diol intermediate, yielded 9,10,11,12,21,22,23,24-octaphenyltetrabenzo-[a,c,n,p]hexacene (4). Crystallographic analysis of hexacene 4 showed it to possess a longitudinal twist of 184°, which was in good agreement with AM1 calculations. In addition to being the most twisted acene synthesized to this point, compound 4 contains within its substructure the most twisted naphthalene, anthracene, tetracene, and pentacene moieties described.

Estimation of Properties of a Photoinitiated Silorane-based Composite with Potential for Orthopaedic Applications

We have synthesized a filler-reinforced silorane composite that has potential applications in orthopaedic surgery, such as for a bone stabilizer. The purpose of the present work was to develop a method for estimating four properties of this material; namely, maximum exotherm temperature, flexural strength, flexural modulus, and fracture toughness. The method involved the use of mixture design-of-experiments and regression analysis of results obtained using 23 formulations of the composite. We validated the estimation method by showing that, for each of four composite formulations that were not included in the method development, the value of each of the aforementioned properties was not significantly different from that obtained experimentally. Our estimation method has the potential for use in the development of a wide range of orthopaedic materials.