Within the limited number of reports on n-type polymers, naphthalene-diimide (NDI) and perylene diimide alternating main chain copolymers are currently evolving as an intriguing class of electron-conducting materials with electron-mobility up to 0.85 cm2/Vs. Typically, conventional step-growth polycondensations are used to synthesize rylene diimide based alternating copolymers, which result in a limited control over polymer MW and polydispersities.

We found out that activated Zn powder and Br-TNDIT-Br form anion-radical complexes instead of Br-TNDIT-ZnBr, conventional Zn-organic derivatives. These highly unusual zinc complexes undergo Ni-catalyzed chain-growth polymerization leading to conjugated polymer P(TNDT) with  controlled MW, relatively narrow PDI and specific end-functions. semiconductors

Figure 1. Preparation of the Br-TNDIT-Br/Zn radical-anion monomer and its polymerization to Ph/H P(TNDT).


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