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Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by “4 + 2” Phenyl Ligands
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-20 , DOI: 10.1021/jacs.2c11511 Xing Huang 1 , Shuai Fu 2 , Cong Lin 3 , Yang Lu 1 , Mingchao Wang 1 , Peng Zhang 1 , Chuanhui Huang 1 , Zichao Li 4 , Zhongquan Liao 5 , Ye Zou 6 , Jian Li 7 , Shengqiang Zhou 4 , Manfred Helm 4 , Petko St Petkov 8 , Thomas Heine 1 , Mischa Bonn 2 , Hai I Wang 2 , Xinliang Feng 1, 9 , Renhao Dong 1, 10
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-20 , DOI: 10.1021/jacs.2c11511 Xing Huang 1 , Shuai Fu 2 , Cong Lin 3 , Yang Lu 1 , Mingchao Wang 1 , Peng Zhang 1 , Chuanhui Huang 1 , Zichao Li 4 , Zhongquan Liao 5 , Ye Zou 6 , Jian Li 7 , Shengqiang Zhou 4 , Manfred Helm 4 , Petko St Petkov 8 , Thomas Heine 1 , Mischa Bonn 2 , Hai I Wang 2 , Xinliang Feng 1, 9 , Renhao Dong 1, 10
Affiliation
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Electrically conductive coordination polymers and metal–organic frameworks are attractive emerging electroactive materials for (opto-)electronics. However, developing semiconducting coordination polymers with high charge carrier mobility for devices remains a major challenge, urgently requiring the rational design of ligands and topological networks with desired electronic structures. Herein, we demonstrate a strategy for synthesizing high-mobility semiconducting conjugated coordination polymers (c-CPs) utilizing novel conjugated ligands with D2h symmetry, namely, “4 + 2” phenyl ligands. Compared with the conventional phenyl ligands with C6h symmetry, the reduced symmetry of the “4 + 2” ligands leads to anisotropic coordination in the formation of c-CPs. Consequently, we successfully achieve a single-crystalline three-dimensional (3D) c-CP Cu4DHTTB (DHTTB = 2,5-dihydroxy-1,3,4,6-tetrathiolbenzene), containing orthogonal ribbon-like π–d conjugated chains rather than 2D conjugated layers. DFT calculation suggests that the resulting Cu4DHTTB exhibits a small band gap (∼0.2 eV), strongly dispersive energy bands near the Fermi level with a low electron-hole reduced effective mass (∼0.2m0*). Furthermore, the four-probe method reveals a semiconducting behavior with a decent conductivity of 0.2 S/cm. Thermopower measurement suggests that it is a p-type semiconductor. Ultrafast terahertz photoconductivity measurements confirm Cu4DHTTB’s semiconducting nature and demonstrate the Drude-type transport with high charge carrier mobilities up to 88 ± 15 cm2 V–1 s–1, outperforming the conductive 3D coordination polymers reported till date. This molecular design strategy for constructing high-mobility semiconducting c-CPs lays the foundation for achieving high-performance c-CP-based (opto-)electronics.
中文翻译：
由“4 + 2”苯基配体实现的具有高电荷迁移率的半导体共轭配位聚合物
导电配位聚合物和金属有机框架是用于（光）电子学的有吸引力的新兴电活性材料。然而，为器件开发具有高电荷载流子迁移率的半导体配位聚合物仍然是一个重大挑战，迫切需要合理设计具有所需电子结构的配体和拓扑网络。在此，我们展示了一种利用具有D 2 h对称性的新型共轭配体（即“4 + 2”苯基配体）合成高迁移率半导体共轭配位聚合物 (c-CP) 的策略。与传统的C 6 h苯基配体相比对称性，“4 + 2”配体的对称性降低导致 c-CP 形成中的各向异性配位。因此，我们成功地获得了单晶三维 (3D) c-CP Cu 4 DHTTB (DHTTB = 2,5-dihydroxy-1,3,4,6-tetrathiolbenzene)，包含正交带状 π- d共轭链而不是二维共轭层。DFT 计算表明，由此产生的 Cu 4 DHTTB 具有小带隙 (~0.2 eV)、费米能级附近的强色散能带以及低电子空穴减少的有效质量 (~0.2 m 0 *). 此外，四探针法揭示了具有 0.2 S/cm 的良好电导率的半导体行为。热电势测量表明它是一种 p 型半导体。超快太赫兹光电导测量证实了 Cu 4 DHTTB 的半导体性质，并证明了 Drude 型传输具有高达 88 ± 15 cm 2 V –1 s –1的高电荷载流子迁移率，优于迄今为止报道的导电 3D 配位聚合物。这种用于构建高迁移率半导体 c-CP 的分子设计策略为实现基于 c-CP 的高性能（光）电子学奠定了基础。
更新日期：2023-01-20
中文翻译：
由“4 + 2”苯基配体实现的具有高电荷迁移率的半导体共轭配位聚合物
导电配位聚合物和金属有机框架是用于（光）电子学的有吸引力的新兴电活性材料。然而，为器件开发具有高电荷载流子迁移率的半导体配位聚合物仍然是一个重大挑战，迫切需要合理设计具有所需电子结构的配体和拓扑网络。在此，我们展示了一种利用具有D 2 h对称性的新型共轭配体（即“4 + 2”苯基配体）合成高迁移率半导体共轭配位聚合物 (c-CP) 的策略。与传统的C 6 h苯基配体相比对称性，“4 + 2”配体的对称性降低导致 c-CP 形成中的各向异性配位。因此，我们成功地获得了单晶三维 (3D) c-CP Cu 4 DHTTB (DHTTB = 2,5-dihydroxy-1,3,4,6-tetrathiolbenzene)，包含正交带状 π- d共轭链而不是二维共轭层。DFT 计算表明，由此产生的 Cu 4 DHTTB 具有小带隙 (~0.2 eV)、费米能级附近的强色散能带以及低电子空穴减少的有效质量 (~0.2 m 0 *). 此外，四探针法揭示了具有 0.2 S/cm 的良好电导率的半导体行为。热电势测量表明它是一种 p 型半导体。超快太赫兹光电导测量证实了 Cu 4 DHTTB 的半导体性质，并证明了 Drude 型传输具有高达 88 ± 15 cm 2 V –1 s –1的高电荷载流子迁移率，优于迄今为止报道的导电 3D 配位聚合物。这种用于构建高迁移率半导体 c-CP 的分子设计策略为实现基于 c-CP 的高性能（光）电子学奠定了基础。
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