The pseudo-octahedral
molybdenum benzylidyne complex [TolC≡Mo(ONO)(OR)]·KOR (R = CCH3(CF3)2) 1, featuring a stabilizing ONO pincer ligand, initiates
the controlled living polymerization of strained dibenzocyclooctynes
at T > 60 °C to give high molecular weight
polymers
with exceptionally low polydispersities (PDI ∼ 1.02). Kinetic
analyses reveal that the growing polymer chain attached to the propagating
catalyst efficiently limits the rate of propagation with respect to
the rate of initiation (kp/ki ∼ 10–3). The reversible coordination
of KOCCH3(CF3)2 to the propagating
catalyst prevents undesired chain-termination and -transfer processes.
The ring-opening alkyne metathesis polymerization with 1 has all the characteristics of a living polymerization and enables,
for the first time, the controlled synthesis of amphiphilic block
copolymers via ROAMP.
Two soluble isomeric acceptor molecules based on a triptycene core, which is connected to three aroylenimidazole units are described. Due to the inherent threefold axis, the molecules are soluble and thus could be fully photophysically characterized in solution and film. Additionally, the preliminary results of these acceptors in organic photovoltaic devices with two different donor materials are reported.
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