Publication date: Apr 01, 2022
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.
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Fig. 3 and Fig. 4.zip
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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
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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
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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
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433.0 KiB | Open data for Fig. S4-5 in the SI. Fig. S4-5:EPR and SQUID measurement. |
Fig. S6-9.zip
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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
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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
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57.6 KiB | Open data for Fig. S17-19 in the Manuscript. Fig. S17-19: DFT calculations of oligomers and dimers. |
Fig. S21.zip
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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
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367.3 KiB | Open data for Fig. S25-29 in the SI. Fig. S25-29: OFET device characterization. |
Fig. S31-34.zip
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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. |
2022.46 (version v1) [This version] | Apr 01, 2022 | DOI10.24435/materialscloud:58-27 |