Electrochemical Investigations of the N‑Type Semiconducting Polymer P(NDI2OD-T2) and Its Monomer: New Insights in the Reduction Behavior Daniel Trefz Adrian Ruff Roman Tkachov Matthias Wieland Miriam Goll Anton Kiriy Sabine Ludwigs 10.1021/acs.jpcc.5b05756.s001 https://acs.figshare.com/articles/journal_contribution/Electrochemical_Investigations_of_the_N_Type_Semiconducting_Polymer_P_NDI2OD_T2_and_Its_Monomer_New_Insights_in_the_Reduction_Behavior/2124022 This manuscript provides the first systematic characterization of the electrochemical properties of the high mobility n-type polymer poly­{[<i>N</i>,<i>N</i>′-bis­(2-octyldodecyl)-naphthalene-1,4,5,8-bis (dicarboximide)-2,6-diyl]-<i>alt</i>-5,5′-(2,2′-bithiophene)} (P­(NDI2OD-T2)) and its corresponding monomer 2,6-bis­(2-bromothien-5-yl)­naphthalene-1,4,5,8-tetracarboxylic-<i>N</i>,<i>N</i>′-bis­(2-octyldodecyl) diimide (Br-NDI2OD-T2-Br) by cyclic voltammetry and in situ spectroelectrochemistry. Both monomer and polymer reveal a 2-fold reduction to the dianion via a radical anion species. The comparison between monomeric and polymeric species allows the explanation of the electrochemical behavior of P­(NDI2OD-T2) according to redox polymers with localization of charges on the naphthalene bisimide unit. Measurements with electrolyte gated transistors suggest electron hopping transport according to mixed valence conductivity. In the last section of this paper we discuss a significant first cycle effect upon electrochemical reduction which had not been reported for n-type polymers before. The effect is even more pronounced for samples with controlled morphology, that is, high amounts of aggregation in the films. In agreement with solution experiments we attribute the appearance of the signal at −1.04 V (<i>E</i><sub>1/2</sub> = −1.00 V) to the radical anion form of the solvated species. 2015-10-08 00:00:00 monomer cyclic voltammetry electrochemical properties solvated species Electrochemical Investigations anion form redox polymers anion species New Insights 2OD electrolyte gated transistors Reduction BehaviorThis manuscript naphthalene bisimide unit cycle effect valence conductivity electrochemical behavior solution experiments electrochemical reduction