Xue Tianhao, Guntermann Roman, Biewald Alexander, Blätte Dominic, Medina Dana D, Hartschuh Achim, Bein Thomas
Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU), Butenandtstraße 5-13, 81377 Munich, Germany.
ACS Appl Mater Interfaces. 2024 Sep 11;16(36):48085-48093. doi: 10.1021/acsami.4c09286. Epub 2024 Aug 28.
Dibenzo[,]chrysene can be viewed as a constrained propeller-shaped tetraphenylethylene with reduced curvature and has been utilized to construct dual-pore kagome covalent organic frameworks (COFs) with tightly packed two-dimensional (2D) layers owing to its rigid and more planar structural characteristics. Here, we introduce 2D COFs based on the node 4,4',4″,4‴-(dibenzo[,]chrysene-2,7,10,15-tetraphenyl)tetraamine (DBCTPTA) featuring extended conjugation compared to the dibenzo[,]chrysene-3,6,11,14-tetraamine (DBCTA) node. We establish two exceptionally crystalline imine-linked 2D COFs with a hexagonal dual-pore kagome structure based on the DBCTPTA core. The newly synthesized thienothiophene (TT) and benzodithiophene (BDT)-based DBCTPTA COFs show a tight stacking behavior between adjacent layers. Furthermore, we obtained an unprecedented, interpenetrated electron-donor/acceptor host-guest system with an electron-donating BDT DBCTPTA COF synthesized with the soluble fullerene derivative [6,6]-phenyl-C-butyric acid methyl ester (PCBM) serving as molecular acceptor. The BDT DBCTPTA COF@PCBM film shows a much shorter amplitude-averaged PL lifetime of 7 ± 2 ps compared to 30 ± 4 ps of the BDT DBCTPTA COF film, indicating the light-induced charge transfer process. The successful formation of interpenetrated donor-acceptor heterojunctions within 2D COFs offers a promising strategy for establishing D-A heterojunctions in diverse framework materials with open channel systems.
二苯并[，]屈可被视为一种曲率减小的受限螺旋桨状四苯乙烯，由于其刚性和更平面的结构特征，已被用于构建具有紧密堆积二维（2D）层的双孔戈薇共价有机框架（COF）。在这里，我们介绍了基于节点4,4'，4″，4‴-（二苯并[，]屈-2,7,10,15-四苯基）四胺（DBCTPTA）的2D COF，与二苯并[，]屈-3,6,11,14-四胺（DBCTA）节点相比，其具有扩展的共轭结构。我们基于DBCTPTA核心建立了两种具有六边形双孔戈薇结构的异常结晶的亚胺连接2D COF。新合成的基于噻吩并噻吩（TT）和苯并二噻吩（BDT）的DBCTPTA COF在相邻层之间表现出紧密堆积行为。此外，我们获得了一种前所未有的互穿电子供体/受体主客体系统，其中合成的具有供电子性的BDT DBCTPTA COF与可溶性富勒烯衍生物[6,6]-苯基-C-丁酸甲酯（PCBM）作为分子受体。与BDT DBCTPTA COF薄膜的30±4 ps相比，BDT DBCTPTA COF@PCBM薄膜的平均振幅PL寿命短得多，为7±2 ps，这表明了光诱导电荷转移过程。在2D COF中成功形成互穿的供体-受体异质结为在具有开放通道系统的各种框架材料中建立D-A异质结提供了一种有前景的策略。
