Synthesis of carbyne analogues by cathodic electrolysis of hexachlorobutadiene

Hexachloro-1,3-butadiene was potentiostatically electrolyzed (−2.0 V vs. SCE) or galvanostatically electrolyzed (1 mA cm−2) with a Pt cathode at 0°C in DMF containing tetrabutylammonium perchlorate as an electrolyte, giving insoluble black fragile films deposited on the electrode. The surface morphology was globular observed by SEM. Electrical conductivity of the pristine film obtained by the potentiostatic method was about 5 × 10−8 S cm−1 which increased to 5 × 10−5 S cm−1 by iodine doping. The as-grown film obtained by the galvanostatic method showed an electrical conductivity of 1 × 10−4 S cm−1. Structural analyses of these products by IR, Raman, XRD, ESR, NMR, and elemental analysis data suggested that these products were carbyne analogues n-doped and stabilized by the electrolyte.