Figure S1. The change in heat capacity as a function of polymer concentration in KTZ ASDs (with

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1 PAA ASD Phema ASD PVP ASD Cp (J/g C) Polymer concentration (% w/w) Figure S1. The change in heat capacity as a function of polymer concentration in KTZ ASDs (with each PAA, PHEMA and PVP polymers).

2 Figure S2: Predicted and experimental Tg values of PAA ASDs at high polymer concentrations.

3 Absorbance (arbitrary units) Sodium salt of PAA PAA Wavenumber (cm -1 ) Figure S3: IR spectrum of PAA and its sodium salt. The peak ~ 1568 cm -1 in sodium salt of PAA spectrum is attributed to the carboxylate ion peak due to salt formation. The decrease in intensity of carboxylic acid peak ~ 1730 cm -1 is evident in the sodium salt.

4 Log Tau (s) 1.00E E E+00 PVP PAA Phema -5.00E E E E E E E E Polymer concentration (moles) Figure S4. Relaxation times as a function of polymer concentration expressed in moles.

5 Table S1: VTF parameters and dielectric Tg obtained from the model fitting of relaxation time data. Amorphous Systems Polymer concentration (%) VTF parameter T 0 (K) D Dielectric Tg ( C) Amorphous KTZ PAA ASD PHEMA ASD PVP ASD

6 Figure S5. View of the structure of an H-bonded, gas-phase dimer of isobutyric acid and N- methylimidazole used for DFT calculations of NMR chemical shielding. An energy-minimized structure with a donor-acceptor distance of approximately 2.8 Å is shown. The model includes a single hydrogen bond between the OH donor (designed to mimic PAA) and the nitrogen acceptor (designed to mimic KTZ). For simplicity, the geometry of the model was adjusted before energy minimization to not include an interaction between the carbonyl oxygen and the CH protons. The donor-acceptor distance and H-bonding proton positions were varied in two separate series of DFT calculations of NMR shielding to simulate (1) the effects of H-bonding and (2) the effect of proton transfer from the oxygen to the nitrogen on NMR chemical shieldings and chemical shifts, as described below.

7 σ iso D... A distance (N... O) Figure S6. Results of DFT calculations of NMR chemical shielding performed using the model system depicted in Figure S5. The isotropic chemical shielding (σiso) of 15 N for the nitrogen acceptor N3 is plotted versus donor-acceptor distance (D A distance). The value of σiso is related to that of the isotropic chemical shift (δiso) by the expression: δ iso = σ ref- σ iso 1-σ ref -χ m σ ref - σ iso, where σiso is the chemical shielding of a reference and χm is the magnetic susceptibility. The values for σiso thus differ in sign from δiso, such that higher values for σiso indicate a more shielded environment with a higher ( upfield ) experimental frequency.

8 σ iso D... A distance (N... O) Figure S7. Results of DFT calculations of NMR chemical shielding performed using the model system for the interaction between KTZ and PAA shown in Figure S5. The 13 C σiso for the carbonyl carbon attached to the OH donor is plotted versus D A distance.

9 σ iso Nitrogen-to-hydrogen distance (Å) Figure S8. Results of DFT calculations of NMR chemical shielding performed using the model system for the interaction between KTZ and PAA shown in Figure S5. The 15 N σiso for the nitrogen acceptor N3 is plotted versus nitrogen-to-hydrogen distance, with low values of nitrogen-tohydrogen distance indicating that the proton has transferred to N3 from the carboxylate.

10 σ iso Nitrogen-to-hydrogen distance (Å) Figure S9. Results of DFT calculations of NMR chemical shielding performed using the model system for the interaction between KTZ and PAA shown in Figure S5. The 13 C σiso for the carboxylate donor is plotted versus nitrogen-to-hydrogen distance, with low values of nitrogen-tohydrogen distance indicating that the proton has transferred to N3 from the carboxylate.