To date, the functionalization of the tris(2,4,6-trichlorophenyl)methyl radical (TTM) is restricted to strong electron donating groups, whereas other substituents give only low or no reaction yields. Here, we present the synthesis of a mono-iodized derivative of the protonated TTM precursor (HTTM). It reacts readily in various types of cross-coupling reactions to give access to triphenylmethyl radicals functionalized with the respective electron donating or electron accepting groups. Iodized HTTM overcomes current limitations in accessibility and yield for TTM radicals functionalized with weaker electron donating groups and electron accepting groups, enabling the synthesis of virtually any desired TTM radical derivative. The performance of iodized HTTM is demonstrated by the synthesis of new stable radical compounds that are otherwise not or hardly accessible. Trimethoxyphenyl is introduced as a first nitrogen-free substituent of electron donating strength comparable to carbazole or diphenylamine. As electron accepting groups, we employ motifs such as benzophenone and pyrimidine and study the respective radicals for their optical properties.

迄今为止，三（2,4,6-三氯苯基）甲基自由基（TTM）的官能化仅限于强给电子基团，而其他取代基仅产生低反应产率或没有反应产率。在这里，我们介绍了质子化 TTM 前体 (HTTM) 的单碘化衍生物的合成。它很容易在各种类型的交叉偶联反应中发生反应，从而获得用相应的给电子基团或受电子基团官能化的三苯甲基自由基。碘化 HTTM 克服了目前用较弱的给电子基团和受电子基团官能化的 TTM 自由基在可及性和产率方面的限制，从而能够合成几乎任何所需的 TTM 自由基衍生物。碘化 HTTM 的性能通过合成新的稳定自由基化合物来证明，这些化合物否则无法或难以获得。三甲氧基苯基作为第一个无氮化合物引入给电子强度与咔唑或二苯胺相当的取代基。作为电子接受基团，我们采用二苯甲酮和嘧啶等基序，并研究各自自由基的光学性质。