Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystalline structure on its electrical properties are discussed. On the other hand, the non‐radical derivative (2), which is isostructural with the radical 1, shows an insulating behavior at all measured pressures. The different electronic structures of these two isostructural systems have a direct influence on the conducting properties, as demonstrated by band structure DFT calculations.

中文翻译：

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开壳特征对有机供体-受体自由基二价体的压力诱导电导率的作用

基于中性有机基团的单组分导体受到了广泛的关注，因为未配对的电子可以在不需要先前的掺杂过程的情况下充当电荷载流子。尽管这些系统大多数都是基于离域的平面自由基，但在此我们提出了一个基于四硫富瓦烯（TTF）部分的非平面和自旋局部自由基，该自由基通过共轭桥与全氯三苯甲基（PTM）自由基连接，在应用时表现出半导体行为高压。报告了该中性自由基TTF-Ph-PTM衍生物（1）的合成，电子性质和晶体结构，并讨论了其晶体结构对其电学性质的影响。另一方面，非自由基导数（2与基团1等构的）在所有测得的压力下均表现出绝热行为。这两个同构系统的不同电子结构直接影响导电性能，如能带结构DFT计算所示。