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Thiele's Hydrocarbons (THs) featuring a 9,10‐anthrylene core with switchable geometric and electronic configurations offer exciting possibilities in advanced functional materials. Despite significant advances in main group‐based diradicaloids in contemporary chemistry, main group THs containing an anthrylene cores have remained elusive, primarily due to the lack of straightforward synthetic strategies and the inherent high reactivity of these species. In this study, we utilize an anthracene‐based phosphine synthon to demonstrate, for the first time, a facile and high‐yielding synthetic strategy for robust P‐functionalized overcrowded ethylenes (OCEs) within the TH family. These OCEs feature a non‐symmetric environment, incorporating (thio) xanthyl and phosphaalkene termini. We systematically probe the electronic structures of these derivatives to illustrate the impact of the isolobal phosphaalkene motif on the quinoidal/diradicaloid character. Notably, the compounds exhibit dynamic redox behavior, leading to orthogonally twisted conformational changes upon oxidation, with a kinetically locked redox‐couple. [ABSTRACT FROM AUTHOR]

Herein we report the reactions of 3,4,5,6‐tetrafluoroterephthalonitrile (1) with bis(silylene) and bis(germylene) LE−EL [E=Si (2) and Ge(3): L=PhC(NtBu)2)]. The reaction of LSi−SiL (L=PhC(NtBu)2) (2) with two equivalents of 1 resulted in an unprecedented oxidative addition of a C−F bond of 1 leading to disilicon(III) fluoride {L(4‐C8F3N)FSi−SiF(4‐C8F3N)L}(4), wherein the Si−Si single bond was retained. In contrast, the reaction of LGe−GeL (L=PhC(NtBu)2) (3) with one equivalent of 1 resulted in the oxidative cleavage of Ge−Ge bond leading to L(4‐C8F3N2)Ge (5) and LGeF (6). All three compounds (4–6) were characterized by NMR spectroscopy, EI‐MS spectrometry, and elemental analysis. X‐ray single‐crystal structure determination of compound 4 unequivocally established that the SiIII−SiIII bond remains uncleaved. [ABSTRACT FROM AUTHOR]