Polymers Composed of Alternating Anthracene and Pyridine Containing Units by Radical Ring-Opening Polymerization: Controlled Synthesis, Optical Properties, and Metal Complexes

Abstract

Novel polymers composed of alternating anthracene and pyridine containing units were synthesized by radical ring-opening polymerization of pyridine-containing cyclic monomers via reversible addition− fragmentation chain transfer (RAFT) process. The ring-opening polymerization proceeded predominantly to afford well-defined polymers (M w /M n ∼ 1.30), which exhibited the characteristic absorption and fluorescence due to the anthracene unit. On the other hand, fluorescence quenching was observed in chloroform and acidic aqueous solutions. The quenching was explained by charge transfer from the excited anthracene units to the coordinated or protonated pyridine units. Additionally, fluorescence quenching independent of external ambient conditions was conducted by quaternization. In the thin film state, the obtained polymers exhibited fluorescence due to the formation of excimers. The formation of complexes between the anthracene-containing polymers and metal species (Zn, Cu, and Co) led to the change in the optical properties compared to those of pristine polymers. These results demonstrate that the unique optical properties could be developed under various conditions due to the interactions between the anthracene and pyridine units in the well-defined polymers.

Monte Carlo Simulations of the Phase Separation of a Copolymer Blend in a Thin Film

“…This lamellar-in-lamellar structure is very similar to those found in multiblock copolymer self-assembly, [21][22][23][24][25][26][27][28][29] while the alternating and block copolymers in our copolymer blend system are much easier to be synthesized than that of asymmetric multiblock copolymers. [30][31][32] In this contribution, to explore the influence of system parameters such as segment distribution and segregation strength on phase separation, we design a series of polymer Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail.…”

Simultaneous Control over Monomer Sequence and Molecular Weight Using the RAFT Process

“…An example is presented by Mori and coworkers, who reported the radical ring-opening polymerization of 10-methylene-9,10-dihydroanthryl-9-spirophenylcyclopropane, as well as its p-bromo, p-chloro and pyridine derivatives, which could be controlled with RAFT (68,69). The resulting polymer contains alternating sequences of anthracene and styrene (derived) moieties ( Figure 5).…”

Light‐Responsive Polymer Membranes

“…Interesting photoresponsive molecules are anthracene and its derivatives, used in optoelectronics thanks to their high fluorescence quantum yields . Anthracene is a polycyclic aromatic hydrocarbon, which undergoes photodimerization on exposure to light or heat …”