Synthesis of solubleall-trans oligomers of 2,5-diheptyloxy-p-phenylenevinylene via olefin metathesis

In situ NMR investigations into the ADMET-reaction of 1,4-diheptyloxy-2,5-divinylbenzene via a Schrock-type molybdenum alkylidene complex

“…In the latter case, reaction temperatures higher than ∼60 • C were necessary to achieve satisfying conversions within 24 h. We hypothesized that the oxygen of a side chain was being complexed at the catalyst center, thus causing a stabilization of intermediate species resulting in lower reaction rates [8,10]. Possible species are illustrated in Scheme 4 and show energetically favorable five-membered rings.…”

“…We reported on the acyclic diene metathesis (ADMET) polycondensation of ring-substituted p-divinylbenzenes [7][8][9][10][11]. The products yielded are soluble mono-or 2,5-disubstituted p-phenylene vinylene (PV) oligomers, with all trans configuration and defect-free microstructure.…”

Homologous Series of 2,5‐Diheptyloxy‐p‐Phenylene Vinylene (DHepO‐PV) Oligomers with Vinyl or 1‐Butenyl End Groups: Synthesis, Isolation, and Microstructure

“…In addition to the published synthesis, [8] further possibilities to yield the diheptyloxy-substituted monomers will be presented and discussed elsewhere. [15] ADMET Polycondensation of 2,5-Diheptyloxy-1,4-divinyl-benzene A typical reaction was performed by adding a 7.5 Â 10 À3 M catalyst solution (2.79 Â 10 À2 mmol Mo(NArMe 2 )(CHCMe 2 -Ph)[OCMe(CF 3 ) 2 ] 2 ) in toluene to (500 mg, 1.4 mmol) 1,4-diheptyloxy-2,5-divinyl-benzene.…”

“…The polycondensation was discussed earlier [8] and optimized in this work. The isolation of single oligomers from the condensation mixtures is possible also for larger amounts of oligomers (several grams).…”

“…We reported the synthesis of soluble diheptyloxy-PV oligomers by acyclic diene metathesis (ADMET) of 2,5-diheptyloxy-1,4-divinylbenzene, [8] c resulting in oligomeric product mixtures 2 (Scheme 1). One aim of this work was to yield a series of homologous single oligomers from these mixtures.…”