Liu, YameiYameiLiuZhang, HengHengZhangYu, HongdeHongdeYuLiao, ZhongquanZhongquanLiaoPaasch, SilviaSilviaPaaschXu, ShunqiShunqiXuZhao, RuyanRuyanZhaoBrunner, EikeEikeBrunnerBonn, MischaMischaBonnWang, HaiHaiWangHeine, ThomasThomasHeineWang, MingchaoMingchaoWangMai, YiyongYiyongMaiFeng, XinliangXinliangFeng2023-08-082023-08-082023https://publica.fraunhofer.de/handle/publica/44777810.1002/anie.2023059782-s2.0-85165291265Linear conjugated polymers have attracted significant attention in organic electronics in recent decades. However, despite intrachain π-delocalization, interchain hopping is their transport bottleneck. In contrast, two-dimensional (2D) conjugated polymers, as represented by 2D π-conjugated covalent organic frameworks (2D c-COFs), can provide multiple conjugated strands to enhance the delocalization of charge carriers in space. Herein, we demonstrate the first example of thiophene-based 2D poly(arylene vinylene)s (PAVs, 2DPAV-BDT-BT and 2DPAV-BDT-BP, BDT=benzodithiophene, BT=bithiophene, BP=biphenyl) via Knoevenagel polycondensation. Compared with 2DPAV-BDT-BP, the fully thiophene-based 2DPAV-BDT-BT exhibits enhanced planarity and π-delocalization with a small band gap (1.62 eV) and large electronic band dispersion, as revealed by the optical absorption and density functional calculations. Remarkably, temperature-dependent terahertz spectroscopy discloses a unique band-like transport and outstanding room-temperature charge mobility for 2DPAV-BDT-BT (65 cm2 V-1 s-1), which far exceeds that of the linear PAVs, 2DPAV-BDT-BP, and the reported 2D c-COFs in the powder form. This work highlights the great potential of thiophene-based 2D PAVs as candidates for high-performance opto-electronics.en2D Conjugated COFs2D Poly(Arylene Vinylene)sBand-Like TransportCharge MobilityThiophene Backbonejournal article