Xiao-Xiang Chen^1,2*, Jia-Tong Li^1*, Yu-Hui Fang^2*, Xin-Yu Deng^1*, Xue-Qing Wang^1*, Guangchao Liu^1*, Yunfei Wang^3*, Xiaodan Gu^3*, Shang-Da Jiang^4*, Ting Lei^1,5*

1 Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, School of Materials Science and Engineering, Peking University, Beijing 100871, China.

2 College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.

3 School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, MS 39406, USA.

4 School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China.

5 Beijing Key Laboratory for Magnetoelectric Materials and Devices, Peking University, Beijing 100871, China.

* Corresponding authors emails: xiaoxiangchen@pku.edu.cn, guatong@pku.edu.cn, yhfang@pku.edu.cn, xinyudeng@stu.pku.edu.cn, xqwang@stu.pku.edu.cn, gcliu@pku.edu.cn, yunfei.wang@usm.edu, xiaodan.gu@usm.edu, jiangsd@scut.edu.cn, tinglei@pku.edu.cn

DOI10.24435/materialscloud:58-27 [version v1]

Publication date: Apr 01, 2022

How to cite this record

Xiao-Xiang Chen, Jia-Tong Li, Yu-Hui Fang, Xin-Yu Deng, Xue-Qing Wang, Guangchao Liu, Yunfei Wang, Xiaodan Gu, Shang-Da Jiang, Ting Lei, High-mobility semiconducting polymers with different spin ground states, Materials Cloud Archive 2022.46 (2022), https://doi.org/10.24435/materialscloud:58-27

Description

Organic semiconductors with high-spin ground states are fascinating because they could enable fundamental understanding on the spin-related phenomenon in light element and provide opportunities for organic magnetic and quantum materials. Although high-spin ground states have been observed in some quinoidal type small molecules or doped organic semiconductors, semiconducting polymers with high-spin at their neutral ground state are rarely reported. Here we report three high-mobility semiconducting polymers with different spin ground states. We show that polymer building blocks with small singlet-triplet energy gap (ΔES-T) could enable small ΔES-T gap and increase the diradical character in copolymers. We demonstrate that the electronic structure, spin density, and solid-state interchain interactions in the high-spin polymers are crucial for their ground states. Polymers with a triplet ground state (S = 1) could exhibit doublet (S = 1/2) behavior due to different spin distributions and solid-state interchain spin-spin interactions. Besides, these polymers showed outstanding charge transport properties with high hole/electron mobilities and can be both n- and p-doped with superior conductivities. Our results demonstrate a rational approach to high-mobility semiconducting polymers with different spin ground states.

Materials Cloud sections using this data

Files

File name	Size	Description
Fig. 3 and Fig. 4.zip MD5md5:1d0ad6e0de996ba8f1acd7c81cf4ed2f	504.1 KiB	Open data for Fig. 3 and Fig. 4 in the manuscript. Fig.3 : Calculated potential energy scans (PES) of the dihedral angles φ. Fig 4: Magnetic property characterization and DFT calculation
Fig. 5 and Fig. 6.zip MD5md5:9f2aed0b9004a02f0959fc6546a20939	162.3 KiB	Open data for Fig. 5 and Fig. 6 in the manuscript. Fig. 5: Magnetic characterization for two polymers. Fig. 6: Thin film morphology and device characterization.
Fig. S1-3.zip MD5md5:928db2caa39819b194675fc19e36542e	734.5 KiB	Open data for Fig. S1-3 in the SI. Fig. S1:DFT calculations for the evaluation of polymer building block planarity. Fig. S2-3: The thermal stability, cyclic voltammograms, and inductively coupled plasma (ICP) emission spectroscopy for the trace metal analysis of the polymers
Fig. S4-5.zip MD5md5:9e8e9af688336c22caa55679e241bc77	433.0 KiB	Open data for Fig. S4-5 in the SI. Fig. S4-5：EPR and SQUID measurement.
Fig. S6-9.zip MD5md5:1d1f97211f20434def65b4ccba12d7ee	199.2 KiB	Open data for Fig. S6-9 in the SI. Fig. S6-9: Quantitative EPR measurement for EPR spin susceptibility of p(TDPP-BBT).
Fig. S10-11.zip MD5md5:1ef920493538ec880d421b6da14de73a	694.3 KiB	Open data for Fig. S10-11 in the SI. Fig. S10-11: Temperature-dependent UV-vis absorption spectra of p(TDPP-TQ) and p(TDPP-BBT).
Fig. S17-19.zip MD5md5:119f8c16aa6039fc50a8b63df46e93ce	57.6 KiB	Open data for Fig. S17-19 in the Manuscript. Fig. S17-19: DFT calculations of oligomers and dimers.
Fig. S21.zip MD5md5:f4fb0022a95b683be45fdd14e7d0b807	54.0 KiB	Open data for Fig. S21 in the SI. Fig. S21: Evolution of the binding energy of the cofacially stacked polymer chains with different degrees of translation of one polymer chain along the long axis.
Fig. S25-29.zip MD5md5:b2cfb8b1e261cf4979a2993283b56f2a	367.3 KiB	Open data for Fig. S25-29 in the SI. Fig. S25-29: OFET device characterization.
Fig. S31-34.zip MD5md5:62666bc2a9a1fd023d032c15a7766ac7	676.4 KiB	Open data for Fig. S31-34 in the SI. Fig. S31-34: Polymer doping and electrical conductivity measurement and thin film characterization.

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Keywords

Organic semiconductor High-spin materials High-mobility polymers