Stable Radical Cations and Their π-Dimers Prepared from Ethylene- and Propylene-3,4-dioxythiophene Co-oligomers: Combined Experimental and Theoretical Investigations

5 years ago

Stable Radical Cations and Their π-Dimers Prepared from Ethylene- and Propylene-3,4-dioxythiophene Co-oligomers: Combined Experimental and Theoretical Investigations

Tohru Nishinaga, Yusuke Sotome

Co-oligomers composed of two 3,4-ethylenedioxythiophene (EDOT) units and two or three 3,4-propylenedioxythiophene (ProDOT) units, i.e., 2E2P_Et and 2E3P_Et, were newly synthesized together with the ProDOT trimer 3P_Me. On the basis of cyclic voltammetry, the gaps between the first and second oxidation potentials (ΔE^1–2) of 2E2P_Et and 2E3P_Et were found to be larger than that of the previously synthesized ProDOT tetramer 4P_Hex. These co-oligomers gave the fairly stable radical cations 2E2P_Et^•+ and 2E3P_Et^•+ by chemical oxidation with AgSbF₆. The disproportionation of 2E2P_Et^•+ and 2E3P_Et^•+ into neutral and dicationic species, which was observed for 4P_Hex^•+, was inhibited in accord with the larger ΔE^1–2. Additionally, the formation of the π-dimers (3P_Me)₂²⁺, (2E2P_Et)₂²⁺, and (2E3P_E)₂²⁺ was clearly observed in dichloromethane solution at low temperatures with UV–vis–NIR spectroscopy. Furthermore, the π-dimerization enthalpies of 2E2P_Et^•+ and 2E3P_Et^•+ were greater than that of 3P_Me^•+, suggesting the formation of fully π-contacted structures. The structures of the π-dimers were optimized at the B97D3 method, and the calculated absorption spectra of the π-dimers obtained using TD-DFT methods were in reasonable agreement with the observed ones, supporting the reliability of the calculated structures.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00816

DOI: 10.1021/acs.joc.7b00816