Liu, YannanYannanLiuFu, ShuaiShuaiFuPastoetter, Dominik L.Dominik L.PastoetterKhan, Arafat HossainArafat HossainKhanZhang, YingyingYingyingZhangDianat, ArezooArezooDianatXu, ShunqiShunqiXuLiao, ZhongquanZhongquanLiaoRichter, MarcusMarcusRichterYu, MinghaoMinghaoYuPoložij, MiroslavMiroslavPoložijBrunner, EikeEikeBrunnerCuniberti, GianaurelioGianaurelioCunibertiHeine, ThomasThomasHeineBonn, MischaMischaBonnWang, HaiHaiWangFeng, XinliangXinliangFeng2022-10-122022-10-122022https://publica.fraunhofer.de/handle/publica/42754210.1002/anie.202209762Vinylene-linked two-dimensional covalent organic frameworks (V-2D-COFs) have shown great promise in electronics and optoelectronics. However, only a few reactions for V-2D-COFs have been developed hitherto. Besides the kinetically low reversibility of C=C bond formation, another underlying issue facing the synthesis of V-2D-COFs is the attainment of high ( E )-alkene selectivity to ensure the appropriate symmetry of 2D frameworks. Here, we tailor the E/Z selectivity of the Wittig reaction by employing a proper catalyst (i.e., Cs 2 CO 3 ) to obtain more stable intermediates and evaluate the temperature across the reaction barrier. Subsequently, the Wittig reaction is innovatively utilized for the synthesis of four crystalline V-2D-COFs by combining aldehydes and ylides. Importantly, the efficient conjugation and decent crystallinity of the resultant V-2D-COFs are demonstrated by their high charge carrier mobilities over 10 cm 2 V -1 s -1 , as revealed by non-contact terahertz (THz) spectroscopy.en2D Conjugated PolymerTerahertzTwo-dimensional Organic FrameworkVinylene-linkageWittig reactionjournal article