Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by “4 + 2” Phenyl Ligands

Huang X, Fu S, Lin C, Lu Y, Wang M, Zhang P, Huang C, Li Z, Liao Z, Zou Y, Li J, Zhou S, Helm M, Petkov PS, Heine T, Bonn M, Wang HI, Feng X, Dong R (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 145

Pages Range: 2430-2438

Journal Issue: 4

DOI: 10.1021/jacs.2c11511

Abstract

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.

Involved external institutions

Technische Universität Dresden DE Germany (DE) Max-Planck-Institut für Polymerforschung (MPI-P) / Max Planck Institute for Polymer Research DE Germany (DE) Hong Kong Polytechnic University (PolyU) CN China (CN) Helmholtz-Zentrum Dresden-Rossendorf (HZDR) DE Germany (DE) Fraunhofer-Institut für Keramische Technologien und Systeme (IKTS) DE Germany (DE) Chinese Academy of Sciences (CAS) / 中国科学院 CN China (CN) Royal Institute of Technology / Kungliga Tekniska Högskolan (KTH) SE Sweden (SE) Sofia University "St. Kliment Ohridski" / Софийски университет "Св. Климент Охридски" BG Bulgaria (BG)

How to cite

APA:

Huang, X., Fu, S., Lin, C., Lu, Y., Wang, M., Zhang, P.,... Dong, R. (2023). Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by “4 + 2” Phenyl Ligands. Journal of the American Chemical Society, 145(4), 2430-2438. https://dx.doi.org/10.1021/jacs.2c11511

MLA:

Huang, Xing, et al. "Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by “4 + 2” Phenyl Ligands." Journal of the American Chemical Society 145.4 (2023): 2430-2438.

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