Spin-Dependent Regulation of The Electronic and Magnetic Properties of Poly(3-Alkylthiophene) Oligomers and Their Composites with Aromatic Nanoadditives

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The energy and spin parameters of poly(3-alkylthiophene) oligomers and their composites with aromatic hydrocarbons are calculated. The coexistence of polarons with different degrees of delocalization in the studied compounds has been identified. Periodic changes in the electronic and spin properties of composites were detected, initiated by the interaction of oligomers with aromatic nanoadditives. The anisotropic parameters of the spin Hamiltonians of the studied systems are obtained and their high-resolution EPR spectra are calculated.

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V. Krinichny

Federal Research Center for Problems of Chemical Physics and Medical Chemistry of the Russian Academy of Sciences

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Email: kivi@icp.ac.ru
俄罗斯联邦, Chernogolovka

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2. Fig. 1. Oligomers of poly(3-alkylthiophenes) (P3AT), poly(3-hydrothiophene) (1, P3HyT, m = 0), poly(3-methylthiophene) (2, P3MeT, m = 1), poly(3-ethylthiophene) (3, P3EtT, m = 2), poly(3-butylthiophene) (4, P3BuT, m = 4), poly(3-hexylthiophene) (5, P3HxT, m = 6), poly(3-octylthiophene) (6, P3OcT, m = 8), poly(3-decylthiophene) (7, P3DeT, m = 10) and poly(3-dodecylthiophene) (8, P3DoT, m = 12), as well as quasi-one-dimensional (Q1D) polyacenes (RA) and quasi-two-dimensional (Q2D) graphene-like polycyclic aromatic hydrocarbons (PH) with different numbers of phenyl rings used in the present work

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3. Fig. 2. Dependence of the forbidden band width Eg = EHOMO - ELUMO of oligomers P3HyT (1), P3MeT (2), P3EtT (3), P3BuT (4), P3HxT (5), P3OcT (6), P3DeT (7) and P3DoT (8) with different number of monomers n and length of alkyl substituents m, optimised within the framework of the density functional theory (DFT) formalism/density functional theory (DFT), in the Malliken/Mulliken approximation in the Orca package environment according to the procedure described in the Methodology section. In the upper part, schematic structures of positively and negatively charged polarons on the P3AT chains with their corresponding energy sublevels in the forbidden zone of the oligomer are shown. The lines show the dependences calculated from Equation (1) at (top to bottom) a0 = 2.761 eV, b = 5.447 eV, c = 1.669, a0 = 2.078 eV, b = 5.886 eV, c = 1.671, a0 = 0.347 eV, b = 5.029 eV, c = 3.153, and a0 = 0.050 eV, b = 4.003 eV, c = 3.650, respectively

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4. Fig. 3. Relative variation of charge (a, c, e) and spin (b, d, f) densities on hydrogen 1H (circles), sulfur 32S (triangles) and carbon 12C (squares) nuclei located along the main x-axis within the polaron of the oxidised poly(3-methylthiophene) oligo12mer (schematically shown from above), optimised within the framework of the density functional formalism/theory, calculated by the Malliken method in the Orca software environment following the procedure described in the Methodology section. For comparison, the corresponding parameters previously calculated for sulfur atoms of the oligo12mer P3HyT [16] are shown as open triangles on (c, d)

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5. Fig. 4. Dependence of isotropic spin-spin hyperfine interaction constant, Aiso, and g-factor, giso, of polaron charge carriers initiated on the chains of oligomers P3HyT (1), P3MeT (2), P3EtT (3), P3BuT (4), P3HxT (5), P3OcT (6), P3DeT (7) and P3DoT (8) from the number of their monomer units n and the length m of their alkyl substituents, optimised and calculated in the Orca software package environment according to the procedure described in the Methodology section. The inset shows the D-band polaron EPR spectra calculated using EasySpin software and the Aiso and giso constants of the indicated oligomers collected in Table 2. The upper and lower solid lines show the dependencies calculated from Equation (1) with a0 = 2.00162, b = 8.71 - 104, c = 5.31 and a0 = 0.471 MHz, b = 83.62 MHz, c = 1. 17, respectively, and the dashed upper and lower lines show the dependencies calculated from the same equation with a0 = 2.00189, b = 6.41×104, c = 2.79 and a0 = 1.873 MHz, b = 81.31 MHz, c = 0.976, respectively

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6. Fig. 5. (a) Change in the band gap of the oligo7mer complex P3HyT:PA (1) and P3HyT:PH (2) depending on the number of phenyl rings n; (b) spin density on sulfur nuclei 32S within the extended polaron of composites P3HyT:PA (1) and P3HyT:PH (2) as a function of n. The upper and lower lines on the tab show the EPR spectra of the D-range complexes P3HyT:PA1 and P3MeT:PA1, respectively, calculated using data from Table 4; (c) the band gap of aromatic Q1D PA and Q2D PH molecules depending on the number of their phenyl rings n. The dotted line shows the dependence calculated from equation (1) with a0 = 0.532 eV, b = 8.968 eV and c = 2.647. The structurally optimized P3HyT:PA7 complex is shown in the upper part as an example

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