TY - JOUR
T1 - Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by “4 + 2” Phenyl Ligands
AU - Huang, Xing
AU - Fu, Shuai
AU - Lin, Cong
AU - Lu, Yang
AU - Wang, Mingchao
AU - Zhang, Peng
AU - Huang, Chuanhui
AU - Li, Zichao
AU - Liao, Zhongquan
AU - Zou, Ye
AU - Li, Jian
AU - Zhou, Shengqiang
AU - Helm, Manfred
AU - St. Petkov, Petko
AU - Heine, Thomas
AU - Bonn, Mischa
AU - Wang, Hai I.
AU - Feng, Xinliang
AU - Dong, Renhao
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/2/1
Y1 - 2023/2/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85146912753&partnerID=8YFLogxK
U2 - 10.1021/jacs.2c11511
DO - 10.1021/jacs.2c11511
M3 - Journal article
C2 - 36661343
AN - SCOPUS:85146912753
SN - 0002-7863
VL - 145
SP - 2430
EP - 2438
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -