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Experimental and theoretical investigations demonstrated that increasing the lactone group density by increasing the benzene content from 0\u2009% benzene (P\u20100), to 50\u2009% (P\u201050), and 75\u2009% (P\u201075) resulted in progressively larger electron affinities (up to 4.37\u2005eV), suggesting a more favorable doping process, when employing (N\u2010DMBI) as the dopant. Larger polaron delocalization was also evident, due to the more planarized conformation, which is proposed to lead to a lower hopping energy barrier. As a consequence, the electrical conductivity increased by three orders of magnitude, to achieve values of up to 12\u2005S\u2009cm and Power factors of 13.2 \u03bcWm<jats:sup>\u22121<\/jats:sup>\u2005K<jats:sup>\u22122<\/jats:sup>were thereby enabled. 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