2,3,7,8,12,13-Hexakis[2-(2-methoxyethoxy)ethoxy]tricycloquinazoline: a discogen which allows enhanced levels of n-doping

A synthesis has been developed for 2,3,7,8,12,13-hexakis[2-(2-methoxyethoxy)ethoxy]-tricycloquinazoline (TCQ6EO2M) in which the ethylenoxy side chains are introduced before elaboration of the heterocylic core. This discogen gives a hexagonal columnar phase (Col_h) between 77 and 233°C. n-Doping using potassium metal is facilitated firstly by the electron poor/π-deficient nature of the core and secondly by the polyethylenoxy side chains which complex the potassium K⁺ counter-ions. The conductivity of the Col_h phase of TCQ6EO2M doped with 10 mol % potassium (σ _∥ = 1.1 x 10^-3 S m^-1) is substantially higher than that previously reported for 2,3,7,8,12,13-hexa(hexylthio)tricycloquinazoline doped with 6 mol % potassium (σ _∥ = 2.9 x 10^-5 S m^-1). Photoconductivity studies of TCQ6EO2M using a time of flight sample configuration show transient photocurrents for both holes and electrons. From these an upper limit on the mobility for the electrons is estimated as ~10^-4 cm² V^-1 s^-1 at 150°C which is of the same magnitude as that for hole mobilities in other columnar discotic liquid crystals.     

A simple route to derivatives of benzo[j]fluoranthene

3,6,8,11-Tetramethoxybenzo[j]fluoranthene can be made from 1,6-dimethoxynaphthalene in a one-pot ferric chloride oxidation/methanol reduction procedure. The reaction is tolerant of the presence of substituents in the 7-position of the naphthalene nucleus and provides a quick and easy route to these particular benzo[j]fluoranthenes. The reactions presumably proceed through initial formation of a bond between the 4-positions of two naphthalene molecules followed by closure of the five-membered ring. Indeed in one case some 4,4′-binaphthyl was isolated from the reaction mixture and it was generally found that better yields of the benzo[j]fluoranthrenes were obtained starting from the 4,4′-binaphthyl rather than by using the naphthalene as the starting material. In an analogous manner to the ring-closure of the 4,4′-binaphthyls, starting from a hexakisalkoxyphenylnaphthalene, a hexakisalkoxyfluoranthene could be obtained.     

Rapid crack growth in a thermoelastic solid under mixed-mode thermomechanical loading

A two-dimensional steady-sate analysis of semi-infinite brittlecrack growth at a constant subcritical rate in an unboundedfully-coupled thermoelastic solid under mixed-mode thermomechanicalloading is made. The loading consists of normal and shear tractionsand heat fluxes applied as point sources (line loads in theout-of-plane direction). A related problem is solved exactly in an integral transformspace, and robust asymptotic forms used to reduce the originalproblem to a set of integral equations. The equations are partiallycoupled and exhibit operators of both Cauchy and Abel types,yet can be solved analytically. The temperature change field at a distance from the moving crackedge is then constructed, and its dominant term is found tobe controlled by the imposed heat fluxes. The role of this termis, indeed, enhanced if the heat fluxes serve to render thecrack as a net heat source/sink for the solid, as opposed tobeing a transmitter of heat across its plane. More generally,the influence of the thermoelastic coupling on this field, aswell as other functions, is found to increase with crack speed.     

A mild photoactivated hydrophilic/hydrophobic switch

Surface modification using light is one of the most powerful methods for controlling the physical and chemical properties offunctionalized surfaces. In this paper, we report on systems where soft UV irradiation (lambda = 365 nm) converts a "low" activity fluorocarbon to a "high" activity amine-functionalized surface. An amine-functionalized SAM (self-assembled monolayer) is first masked using a tertiary amine catalyzed reaction with an N-hydroxysuccinimidyl carbonyl reagent. This mild, room-temperature reaction introduces a hydrophobic photocleavable nitrobenzyl "protecting group" terminated with a fluorocarbon end-chain. UV irradiation (lambda = 365 nm) of this hydrophobic/fluorocarbon surface cleaves the nitrobenzyl residue, returning the surface to the original hydrophilic/amine-functionalized state. This provides a mild, generic method of producing surfaces with hydrophilic/hydrophobic patterns or patterned with amine functional residues. Two different protecting groups, one terminated with a single and the other with three fluorocarbon end chains, are compared. In the case of the more bulky protecting group, only a small proportion of the amine residues react, but the surface is equally hydrophobic and the amine residues equally well shielded from further reaction. Surfaces are characterized by X-ray photoelectron spectroscopy, ellipsometry, surface potential, and contact angle measurements. Images of the photopatterned SAMs were obtained using scanning electron microscopy.