DOI: 10.5061/dryad.9ghx3ffwh
title: Data from: Intrinsic doping and electrostatic complexation of sulfonated poly(3,4-ethylenedioxythiophenes) (PEDOTs)

description: Self-doped conjugated polymers represent a compelling strategy for
 achieving efficient electrostatically complexed ionic networks without the
 need for external dopants. In this work, we present a previously
 unreported class of sulfonated poly(3,4-ethylenedioxythiophene) (PEDOT)
 derivatives that exhibit intrinsic self-doping and readily form stable
 complexes with insulating polyelectrolytes. Notably, we show that even
 minor variations in the side chain structure, such as a one-carbon
 difference, have a profound effect on the polymers’ electrical
 conductivity, structural order, and self-doping level. Using detailed
 spectroscopic and electrochemical analyses, we reveal how these materials
 intrinsically stabilize charge carriers and maintain their conductive
 behavior after complexation. Our findings demonstrate that the self-doped
 sites act as quasi-permanent ionic–electronic dipoles, creating a robust
 and adjustable platform for next-generation soft electronic materials.
 This data includes the raw data of spectroscopy (ultraviolet–visible
 (UV–vis), mass spectrometry (MS), Fourier-transform infrared (FTIR),
 nuclear magnetic resonance (NMR)), electronic (cyclic voltammetry (CV),
 current–voltage (IV) curves of thin films), and thermal properties
 (differential scanning calorimetry (DSC) and thermogravimetric analysis
 (TGA)).
description: # Data from: Intrinsic doping and electrostatic complexation of sulfonated
 poly(3,4-ethylenedioxythiophenes) (PEDOTs) Dataset DOI:
 [10.5061/dryad.9ghx3ffwh](10.5061/dryad.9ghx3ffwh) ## Description of the
 data and file structure This dataset contains the raw (or preliminarily
 processed) data of experimental results collected to publish manuscript:
 "Intrinsic Doping and Electrostatic Complexation of Sulfonated
 Poly(3,4-ethylenedioxythiophenes) (PEDOTs)", authored by Hyunki Yeo,
 Anush Singhal, Alexandra Zele, Rachel A. Segalman, and Michael L.
 Chabinyc.  **Experimental Methods** *pH measurements and UV-vis
 spectroscopy of solutions upon titration.* 1 mM aqueous solution of
 PEDOT-SS-Na was prepared. Titration among adding HCl solution was
 demonstrated with a Mettler Toledo InLab probe connected to a ThermoFisher
 pH meter, while the concentration and output pH were logged. On every
 integer pH, the solution was carried out for Uv-vis measurements using an
 Agilent Cary 60 UV-vis spectrophotometer. *Conductivity Measurements.*
 PEDOT-nS films were prepared by drop-casting a 1 mM aqueous solution onto
 quartz substrates (25 mm × 25 mm × 1 mm). The films were then further
 annealed at 90°C for 30 minutes on a hot plate, followed with vacuum
 overnight. Electrical conductivity measurements were carried out on the
 resulting films (0.5 ~ 1 µm thickness) using the standard four-point probe
 meter (Ossilla, T2001A4). Film thickness was determined in dry air using a
 Bruker Dektak XT stylus profilometer. Complex films were blade coated on
 top of quartz or silicon substrates and followed the same procedure.
 *Cyclovoltammetry Measurements.* CV measurements were carried out with
 potentiostat (Biologic, SP-200), in air in a solution of acetonitrile
 (thin films) with 5 wt % water containing 0.01 M LiTFSI, to be consistent
 with all other measurements conducted under ambient conditions. This
 choice was deliberate to reflect realistic device environments where
 oxygen is inevitably present and to ensure that all redox features
 observed are representative of performance under practical operating
 conditions. Both PEDOT-nS systems exhibited typical redox activity
 consistent with other conjugated polymers, maintaining broad features even
 at scan rates up to 200 mV/s. Adding 5% water to the electrolyte was
 essential for reproducible electrochemistry, but higher water content
 dissolved the polymer films. This balance optimizes dielectric properties
 to enable ion transport while preserving film integrity. *UV-vis-NIR
 spectroscopy of films.* Films used for conductivity measurements were
 directly taken to absorption spectra collection, using an Shimadzu UV3600
 UV-Nir-NIR spectrometer. *Grazing incidence wide angle X-ray scattering
 (GIWAXS).* Identical films for UV-vis-NIR measurements were brought on
 beamline 11–3 at the Stanford Synchrotron Radiation Lightsource (SSRL).
 LaB6 was used as a calibration for the beam center and sample-to-detector
 distance (315 mm). 2D GIWAXS scattering images were collected using 2D
 Rayonix MX225 CCD area detector at an incidence angle of 0.10° with 30 s
 exposure times. The samples were kept under helium during X-ray exposure
 to minimize sample degradation and scattering from O2. The collected data
 was processed using Nika, a 2D data reduction macro on Igor Pro using
 established procedures. *Transmission Small angle X-ray scattering (SAXS)
 and Wide angle X-ray scattering (WAXS).* Dried samples were placed in
 aluminum washers lined with Kapton tape, then the other side of the
 samples were sealed using Kapton tape. Measurements were carried out in a
 home built Next Generation SAXS/WAXS system. *X-ray diffraction (XRD).*
 Polymers prepared in their powder form were loaded on an amorphous silicon
 disk. Measurement was carried out in a Panalytical Empyrean Powder
 Diffractometer. X-ray photoelectron spectroscopy (XPS). Experiments were
 conducted using an Escalab Xi+ Spectrometer (ThermoFisher Scientific)
 equipped with a monochromatic Al Kα X-ray source, operated under an ultra
 high vacuum of approximately 5 × 10-9 mbar. Charge compensation was
 achieved using a dual-mode low energy ion-electron flood gun.
 High-resolution spectra were collected at a pass energy of 20 eV with a
 step size of 0.05 eV (5 times), while survey scans were acquired at 100 eV
 pass energy with 0.5 eV intervals once. *Thermographic analysis (TGA).*
 Thermogravimetric analysis (TGA) data were collected using a TA
 Instruments Q600 SDT Series simultaneous thermal analyzer, and the
 experiments were performed under a helium environment at a gas flow rate
 of 100 mL min-1. Samples were initially held isothermal for 10 min at 20
 ℃, then heated to 800 ℃ at a rate of 10 ℃ min-1. ### Files and variables
 Each file names are associated with the content and description of data.
 File names are formatted as: *"Figure XX_Data Type and
 variables_Material_Sample type".* Plotted figures and type of
 variables, materials, and sample type are also defined in original
 manuscript. **Commonly used variables with abbreviations:** * q: q-factor
 (unit: Å^-1^) in *GIWAXS, WAXS and SAXS raw datafiles* * C: concentration
 (unit: mmol L^-1^) in *concentration* datafiles * V: voltage (unit: V) in
 *CV and conductivity datafiles* * I: current (unit: A) in *CV and
 conductivity datafiles* * E: binding energy (unit: eV) in *XPS datafiles*