No abstract

Dipolar NLO chromophores with an interposed conjugated tetraene segment in which all but four of the methine groups are incorporated into a tetrahydronaphthalene framework have been synthesized and characterized. This conformation-locking approach furnishes NLO chromophores possessing an enhanced thermal stability. X-ray crystallographic data indicate that the polyenic chain of these molecules exhibits a near-planar all-trans conformation in the solid state. EFISH measurements show that these conformationally locked tetraenic chromophores exhibit large second-order optical nonlinearities (µ‚β ∼4000 × 10 -48 cm 6 at 1907 nm), although the nonlinearities of the corresponding "unlocked" analogues are slightly larger.

In this paper the synthesis and characterization of a hyperbranched poly(aryl ether oxazole) with terminal phenolic groups are described. An ABB‘ monomer containing a pair of phenolic groups and an aryl fluoride which is activated toward displacement by the attached oxazole ring was prepared. The nucleophilic substitution of the fluoride with the phenolic group leads to the formation of ether linkage and subsequently the hyperbranched poly(aryl ether oxazole) P1. As determined by a combination of model compound studies and 1H NMR integration experiments, the degree of branching of P1 is approximately 50%. The polymer P1 is thermally stable and readily soluble in polar organic solvents. The terminal phenolic groups in P1 were easily functionalized, yielding hyperbranched polymers with a variety of functional chain ends. Physical properties, such as the glass transition temperature and the solubility of the hyperbranched poly(aryl ether oxazole)s, depended significantly on the nature of the chain ends.