Hyperbranching-Enhanced-Emission Effect Discovered in Hyperbranched Poly(4-(cyanomethyl)phenyl methacrylate)

To disclose the effect of architecture over fluorescence behaviors of polymers, linear and hyperbranched poly(4-(cyanomethyl)phenyl methacrylate)s (PCPMAs) were synthesized by using atom transfer radical polymerization (ATRP). Compared to linear PCPMAs with weakly AIE (AIE: aggregation-induced-emission) characteristics and small-molecule analogues of 4-(cyanomethyl)phenyl isobutyrate (CPB) with ACQ (ACQ: aggregation-caused-quenching) behaviors, hyperbranched PCPMA showed dramatically stronger fluorescence at both solution and solid states and more significant AIE characteristics, which were further enhanced by increasing the branching degree, indicating a significant hyperbranching-enhanced-emission effect (HEE). The HEE effect was attributed to the strong promotion of hyperbranched architecture over the formation of a nitrile group cluster with through-space conjugation (TSC). The HEE effect provided a promising methodology to construct efficient nontraditional fluorescent polymers without large-conjugated, rigid, and planar emitter groups.