1、Introduction 高性能的n型聚合物对于 有机电子学的发展至关重要，但具有优化的物理化学性质的强缺电子构建块仍然有限。酰亚胺功能化多环芳烃（PAHs）具有扩展的π共轭框架，高缺电子性和良好的溶解度，是开发高性能n型聚合物的很有前途的候选材料。在多环芳烃中，菲（PhA）具有良好的芳香π体系功能化。然而，基于pha的酰亚胺的研究很少，主要是由于合成的挑战。在此，
我们报道了两种功能化的PhAs，CPOI和CPCNI，通过同时将酰亚胺与碳基或二亚胺结合到PhA上。值得注意的是，二氰亚甲基修饰的CPCNI表现出良好稳定的LUMO能量水平（-3.84 eV），这归因于酰亚胺和氰基的协同诱导效应。随后，在CPOI和CPCNI的基础上，开发了两种聚合物PCPOI-Tz和PCPCNI-Tz。应用于有机薄膜晶体管中，由于CPCNI的强缺电子特性，聚合物PCPCNI-Tz与PCPOI-Tz相比具有更好的电子迁移率，阈值电压大大降低。这项工作提供了两种结构新颖的缺电子构建块，并强调了具有强吸电子基团的PhAs双功能化对设计n型聚合物的有效性。
2、Introduction to Images and Text
Fig1. (a) Design strategy of dual-functionalized phenanthrenes CPOI and CPCNI. (b) The LUMO energy levels of MeCPOI, MeCPCNI together with the classic imide units as comparison. The LUMO levels are calculated based on density functional theory (DFT) at the B3LYP/6-31G* level, and the side chains on the imide groups are replaced with methyl chains for calculation simplicity.
Scheme 1. Synthetic route to CPOI and CPCNI. Reagents and conditions: i) NaIO4, RuCl3, CH2Cl2/CH3CN/H2O, room temperature; ii)NBS, H2SO4, room temperature; iii) 1,4-dioxane/NaOH (1 M), 100 °C; iv) CuCN,DMF, microwave, 150 °C; v) 70% H2SO4; vi) Ac2O, reflux; vii) a, octan-1-amine, toluene, 110 °C; SOCl2, reflux; b, 2,6-diisopropylaniline, DMAP, 1,4-dioxane, reflux; viii) malononitrile, DMSO, 120 °C.
Fig2. (a) UV-Vis absorption spectra (filled symbols) and PL spectra (λex = 340 nm) (open symbols) in chloroform solution; (b) CV curves of C8CPOI and C8CPCNI measured in THF/0.1 M (n-Bu)4NPF6; Scanning rate: 50 mV s-1 ; (c) DFT-calculated HOMO, LUMO and Eg of MeCPOI and MeCPCNI (black line) and CV characterized energy levels of C8CPOI and C8CPCNI (red line). For DFT calculation, the side chain was replaced with methyl group for calculation simplicity.
Fig3. Single crystal structures and packing modes of the model compounds (a) DIPCPOI and (b) DIPCPCNI.
Scheme 2. Synthetic route to polymers PCPOI-Tz and PCPCNI-Tz. i) Br2, Ag2SO4, 98% H2SO4, 100 °C; ii) Ac2O, reflux; iii) 4-octadecyldocosan-1-amine, toluene, 110 °C; SOCl2, reflux; iv) malononitrile, TiCl4, chlorform/pyridine, room temperature; v) 4,4'-bis(octyloxy)-2,2'-bis(trimethylstannyl)-5,5'-bithiazole, Pd2(dba)3, P(o-tolyl)3, toluene, microwave, 140 °C.
Fig 4. Optimized molecular geometries of the trimers of repeating units of polymers PCPOI-Tz and PCPCNI-Tz. The alkyl chains were replaced with methyl groups for calculation simplicity.
Fig5. (a) UV-Vis absorption spectra (in chloroform solution and film state) and (b) CV curves of polymers PCPOI-Tz and PCPCNI-Tz in CH3CN/0.1 M (n Bu)4NPF6; Scanning rate: 50 mV s-1 .
Fig6. Top-gate/bottom-contact OTFT (a, b) transfer (VD = 80 V) and (c, d) output characteristics of (a, c) PCPOI-Tz and (b, d) PCPCNI-Tz. Device dimension: L = 10 μm, W = 5mm.
Fig7. The GIWAXS and AFM height images (inset) of (a) PCPOI-Tz and (b) PCPCNI-Tz, and in-plane and out-of-plane line-cut profiles of GIWAXS patterns of (c) PCPOI-Tz and (d) PCPCNI-Tz.
3、Paper Information Angewandte Chemie International Edition Functionalized Phenanthrene Imide-Based Polymers for n-TypeOrganic Thin-Film Transistors Jie Yang, Jianfeng Li,Xiage Zhang,Wanli Yang,Sang Young Jeong, Enmin Huang,Bin Liu,Han Young Woo,Zhicai Chena,and Xugang Guo Angew. Chem. Int. Ed. 2024, e202319627 https://doi.org/10.1002/anie.202319627
来源：发光材料与器件应用
