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The monomer 9-[(tert-butyldimethylsilyl)oxy][2.2]paracyclophan-1-ene (1) is polymerized by Mo(NAr)(CHCMe2Ph)(OCMe(CF3)2)2 (Ar = 2,6-diisopropylphenyl) in a living manner. Block copolymers containing poly(1) and polynorbornene (poly(NBE)) can be prepared and have narrow polydispersities. Treatment of poly(1) with NBu4F produces poly(9-hydroxy[2.2]paracyclophan-1-ene) which dehydrates to poly(p-phenylenevinylene) (PPV) under mild conditions. Block copolymers containing segments of size-specific and defect-free PPV with poly(NBE) of various dimensions can be prepared readily and are soluble in a variety of common organic solvents. These polymers serve as excellent candidates to measure the effect of chain length and frequency of interchain contacts on PPV's fluorescence quantum yield (Φf). Solution and solid-state quantum yield determinations, coupled to fluorescence lifetime measurements, reveal an acute drop in Φf as the degree of polymerization of the emissive species increases and as the average distance between PPV chains decreases. PPV x -block-poly(NBE) y prepared in solution consistently shows larger Φf than material prepared by solid-state dehydration. The poly(NBE) companion block also serves to protect PPV from atmospheric degradation.

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A series of bis(vinylthienyl)silane monomers were prepared by reaction of 2 equiv of (vinylthienyl)lithium or (vinylthienyl)magnesium bromide with different dichlorosilicon dialkyls. The monomers react with the Schrock initiator Mo(NAr)(CHCMe2Ph)(OCMe(CF3)2)2 (Ar = 2,6-diisopropylphenyl), via the acyclic diene metathesis polymerization (ADMET) mechanism, to give poly(silanyl−dithienylethene) derivatives in excellent yield. GPC data suggest that the resulting polymers have short repeat sequences. Interchromophore cooperativity is evident, as a low energy emission, for polymer structures that have smaller side groups. This phenomenon is similar to the chromophore cooperativity observed in polymers containing stilbene fragments along the backbone.

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