Compound characterization data — Bazan-Bergamino et al., 2026

Emmanuel A. Bazan-Bergamino, Steven Ayoub, David L. Mobley, Lyle Isaacs. “Sulfated prism[6]arene binds one guest internally and one guest externally.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007937/v1

Pr[6]AS
Melting point	>240 °C (dec.)
IR (ATR, cm⁻¹)	3475w, 1624w, 1599w, 1509w, 1441w, 1400w, 1228s, 1135m, 1056s, 1007s, 850m, 784s, 540m, 615s
¹H NMR (600 MHz, RT, D₂O)	δ 7.98 (d, J = 9.2 Hz, 12H), 7.45 (d, J = 9.2 Hz, 12H), 4.94 (s, 12H)
¹³C NMR (150 MHz, RT, D₂O, NaHCO₃ as internal reference)	δ 142.7, 127.6, 125.3, 121.0, 117.6, 20.4 ppm
¹H and ¹³C NMR symmetry assignment	The ¹H NMR spectrum displayed two aromatic doublets and a singlet for the bridging CH₂ groups; the ¹³C NMR spectrum displayed five aromatic resonances and one bridging-CH₂ resonance at 20.4 ppm; the resonance patterns were assigned to a time-averaged D₆-symmetric conformation
ESI-MS (negative ion mode)	m/z 718.87 ([M − 8SO₃Na + 6H]²⁻), calc. for C₆₆H₄₂O₂₄S₄Na₄²⁻ 719.03; less intense ions at m/z 668 ([M − 9SO₃Na + 7H]²⁻) and 790 ([M − 8SO₃Na + 6H + Na₂SO₄]²⁻)
¹H NMR, ¹³C NMR, ESI-MS and IR spectra	Image data were not transcribed

Pr[6]AS
¹H NMR dilution experiment (600 MHz, 25 °C, D₂O, 0.05–5.0 mM)	Δδ ≤ 0.03 ppm; significant self-association in water was not observed
Variable-temperature ¹H NMR (600 MHz, D₂O, 0.5 mM, 293–343 K)	Spectral sharpening was not observed; Pr[6]AS dynamics were assigned as slow on the chemical-shift timescale
Variable-temperature and dilution ¹H NMR spectra	Image data were not transcribed

Pr[6]AS–guest ¹H NMR complexation-induced chemical-shift changes at a 1:1 host:guest molar ratio
NMe₄	Hk −0.32 ppm
C6DA	Hm −1.69 ppm; Ho −1.99 ppm; Hp −2.74 ppm
Me2C6DA	Hk −0.63 ppm; Hm −1.89 ppm; Ho −1.97 ppm; Hp −2.72 ppm
Me4C6DA	Hk −0.62 ppm; Hm −1.96 ppm; Ho −2.17 ppm; Hp −2.88 ppm
Me6C6DA	Hk −0.64 ppm; Hm −1.75 ppm; Ho −2.42 ppm; Hp −2.97 ppm
PXDA	Hm −1.14 ppm; Ho −1.42 ppm
Me6PXDA	Hk −0.85 ppm; Hm −1.30 ppm; Ho −2.08 ppm
MV	Hk −0.15 ppm; Hm −0.80 ppm; Ho −2.65 ppm
CHDA	Hm −0.72 ppm; Ho −0.82 ppm; Hp −0.77 ppm
Me6CHDA	Hk −1.05 ppm; Hm −1.86 ppm; Ho −2.21 ppm; Hp −2.30 ppm
Bipip	Hm −0.92 ppm; Hn −1.54 ppm; Ho −2.32 ppm; Hp −1.77 ppm; Hq −2.62 ppm
Me4Bipip	Hk −0.42 ppm; Hl −0.92 ppm; Hm −1.08 ppm; Hn −1.39 ppm; Ho −2.28 ppm; Hp −2.36 ppm; Hq −2.58 ppm

Pr[6]AS–Me4Bipip ¹H NMR molar-ratio series
Hq Δδ at 1:1 Pr[6]AS:Me4Bipip	−2.58 ppm
Hq Δδ at 1:2 Pr[6]AS:Me4Bipip	−2.42 ppm
Hq Δδ at 1:3 Pr[6]AS:Me4Bipip	−2.37 ppm
Hq Δδ at 1:4 Pr[6]AS:Me4Bipip	−1.93 ppm
¹H NMR guest-exchange assignment	Guest exchange was assigned to the intermediate-to-fast regime on the chemical-shift timescale; the 1:2 Hq shift was reduced by 6 % relative to the 1:1 shift

Pr[6]AS–guest ¹H NMR spectra (600 MHz, RT, D₂O, 1:1–1:4 host:guest molar ratios)
NMe₄, CHDA, Me6CHDA, PXDA, Me6PXDA, MV, C6DA, Me2C6DA, Me4C6DA, Me6C6DA, Bipip, Me4Bipip and PPCP	Image data were not transcribed

Pr[6]AS–guest ITC series (PBS, pH 7.4, 298 K)
C6DA	Kₐ₁ = (3.58 ± 0.55) × 10⁵ M⁻¹; ΔH₁ = −4.05 ± 0.83 kcal mol⁻¹; Kₐ₂ = (4.00 ± 1.17) × 10⁴ M⁻¹; ΔH₂ = −9.62 ± 1.80 kcal mol⁻¹; β = (1.43 ± 0.47) × 10¹⁰ M⁻²; ΔH₁ + ΔH₂ = −13.67 ± 1.98 kcal mol⁻¹
Me2C6DA	Kₐ₁ = (1.59 ± 0.02) × 10⁶ M⁻¹; ΔH₁ = −7.35 ± 0.09 kcal mol⁻¹; Kₐ₂ = (8.27 ± 0.23) × 10⁴ M⁻¹; ΔH₂ = −14.23 ± 0.33 kcal mol⁻¹; β = (1.31 ± 0.04) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −21.58 ± 0.34 kcal mol⁻¹
Me4C6DA	Kₐ₁ = (8.45 ± 1.00) × 10⁵ M⁻¹; ΔH₁ = −9.35 ± 1.11 kcal mol⁻¹; Kₐ₂ = (3.40 ± 0.18) × 10⁵ M⁻¹; ΔH₂ = −12.37 ± 1.35 kcal mol⁻¹; β = (2.87 ± 0.37) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −21.72 ± 1.75 kcal mol⁻¹
Me6C6DA	Kₐ₁ = (6.42 ± 0.37) × 10⁵ M⁻¹; ΔH₁ = −10.57 ± 0.83 kcal mol⁻¹; Kₐ₂ = (9.49 ± 0.23) × 10⁵ M⁻¹; ΔH₂ = −11.47 ± 1.04 kcal mol⁻¹; β = (6.09 ± 0.38) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −22.14 ± 1.33 kcal mol⁻¹
Me6PXDA	Kₐ₁ = (1.15 ± 0.17) × 10⁶ M⁻¹; ΔH₁ = −5.78 ± 0.83 kcal mol⁻¹; Kₐ₂ = (2.00 ± 0.28) × 10⁵ M⁻¹; ΔH₂ = −8.49 ± 0.63 kcal mol⁻¹; β = (2.30 ± 0.47) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −14.27 ± 1.04 kcal mol⁻¹
MV	Kₐ₁ = (4.48 ± 0.04) × 10⁷ M⁻¹; ΔH₁ = −15.03 ± 0.08 kcal mol⁻¹; Kₐ₂ = (1.55 ± 0.02) × 10⁶ M⁻¹; ΔH₂ = −13.77 ± 0.09 kcal mol⁻¹; β = (6.94 ± 0.12) × 10¹³ M⁻²; ΔH₁ + ΔH₂ = −28.80 ± 0.12 kcal mol⁻¹
Me6CHDA	Kₐ₁ = (1.41 ± 0.03) × 10⁶ M⁻¹; ΔH₁ = −6.36 ± 0.05 kcal mol⁻¹; Kₐ₂ = (2.57 ± 0.04) × 10⁵ M⁻¹; ΔH₂ = −7.56 ± 0.22 kcal mol⁻¹; β = (3.62 ± 0.08) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −13.92 ± 0.23 kcal mol⁻¹
Bipip	Kₐ₁ = (1.11 ± 0.01) × 10⁶ M⁻¹; ΔH₁ = −5.23 ± 0.02 kcal mol⁻¹; Kₐ₂ = (2.09 ± 0.02) × 10⁵ M⁻¹; ΔH₂ = −7.64 ± 0.14 kcal mol⁻¹; β = (2.31 ± 0.03) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −12.87 ± 0.14 kcal mol⁻¹
Me4Bipip	Kₐ₁ = (1.28 ± 0.11) × 10⁶ M⁻¹; ΔH₁ = −12.33 ± 1.15 kcal mol⁻¹; Kₐ₂ = (6.48 ± 0.31) × 10⁵ M⁻¹; ΔH₂ = −12.63 ± 1.42 kcal mol⁻¹; β = (8.29 ± 0.82) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −24.96 ± 1.83 kcal mol⁻¹
PPCP	Kₐ₁ = (1.02 ± 0.08) × 10⁶ M⁻¹; ΔH₁ = −9.08 ± 0.82 kcal mol⁻¹; Kₐ₂ = (1.04 ± 0.13) × 10⁵ M⁻¹; ΔH₂ = −15.77 ± 0.69 kcal mol⁻¹; β = (1.06 ± 0.16) × 10¹¹ M⁻²; ΔH₁ + ΔH₂ = −24.85 ± 1.07 kcal mol⁻¹
Me4Bipip, ITC inflection	Molar ratio ≈2

Pr[6]AS–guest ITC triplicate averages (Pr[6]AS 10 µM, guest 200 µM, PBS, pH 7.4)
Me6CHDA, direct titration	Kₐ₁ = (1.41 ± 0.03) × 10⁶ M⁻¹; ΔH₁ = −6.36 ± 0.05 kcal mol⁻¹; −TΔS₁ = −2.03 ± 0.06 kcal mol⁻¹; Kₐ₂ = (2.55 ± 0.04) × 10⁵ M⁻¹; ΔH₂ = −7.56 ± 0.22 kcal mol⁻¹; −TΔS₂ = 0.18 ± 0.22 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (3.62 ± 0.08) × 10¹¹ M⁻²; ΔH = −13.92 ± 0.23 kcal mol⁻¹; −TΔS = −1.85 ± 0.23 kcal mol⁻¹
Me6PXDA, direct titration	Kₐ₁ = (2.23 ± 0.14) × 10⁶ M⁻¹; ΔH₁ = −5.82 ± 0.31 kcal mol⁻¹; −TΔS₁ = −2.84 ± 0.31 kcal mol⁻¹; Kₐ₂ = (2.31 ± 0.19) × 10⁵ M⁻¹; ΔH₂ = −7.87 ± 0.20 kcal mol⁻¹; −TΔS₂ = 0.55 ± 0.20 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (5.14 ± 0.53) × 10¹⁰ M⁻²; ΔH = −13.69 ± 0.37 kcal mol⁻¹; −TΔS = −2.29 ± 0.37 kcal mol⁻¹
MV, competitive titration	Kₐ₁ = (4.48 ± 0.04) × 10⁷ M⁻¹; ΔH₁ = −15.07 ± 0.08 kcal mol⁻¹; −TΔS₁ = 4.63 ± 0.08 kcal mol⁻¹; Kₐ₂ = (1.55 ± 0.02) × 10⁶ M⁻¹; ΔH₂ = −13.77 ± 0.09 kcal mol⁻¹; −TΔS₂ = 5.32 ± 0.09 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (6.94 ± 0.12) × 10¹³ M⁻²; ΔH = −28.80 ± 0.12 kcal mol⁻¹; −TΔS = 9.95 ± 0.10 kcal mol⁻¹
C6DA, competitive titration	Kₐ₁ = (3.58 ± 0.55) × 10⁵ M⁻¹; ΔH₁ = −4.05 ± 0.83 kcal mol⁻¹; −TΔS₁ = −3.52 ± 0.83 kcal mol⁻¹; Kₐ₂ = (4.00 ± 1.17) × 10⁴ M⁻¹; ΔH₂ = −9.62 ± 1.80 kcal mol⁻¹; −TΔS₂ = 3.34 ± 1.81 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (1.43 ± 0.47) × 10¹⁰ M⁻²; ΔH = −13.67 ± 1.98 kcal mol⁻¹; −TΔS = −0.18 ± 1.98 kcal mol⁻¹
Me2C6DA, competitive titration	Kₐ₁ = (1.59 ± 0.02) × 10⁶ M⁻¹; ΔH₁ = −7.35 ± 0.09 kcal mol⁻¹; −TΔS₁ = −1.11 ± 0.09 kcal mol⁻¹; Kₐ₂ = (8.27 ± 0.23) × 10⁴ M⁻¹; ΔH₂ = −14.23 ± 0.33 kcal mol⁻¹; −TΔS₂ = 7.52 ± 0.33 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (1.31 ± 0.04) × 10¹¹ M⁻²; ΔH = −21.58 ± 0.34 kcal mol⁻¹; −TΔS = 6.41 ± 0.34 kcal mol⁻¹
Me4C6DA, direct titration	Kₐ₁ = (8.45 ± 1.00) × 10⁵ M⁻¹; ΔH₁ = −9.35 ± 1.11 kcal mol⁻¹; −TΔS₁ = 1.27 ± 1.11 kcal mol⁻¹; Kₐ₂ = (3.40 ± 0.18) × 10⁵ M⁻¹; ΔH₂ = −12.37 ± 1.35 kcal mol⁻¹; −TΔS₂ = 4.82 ± 1.35 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (2.87 ± 0.37) × 10¹¹ M⁻²; ΔH = −21.72 ± 1.75 kcal mol⁻¹; −TΔS = 6.09 ± 1.49 kcal mol⁻¹
Me6C6DA, direct titration	Kₐ₁ = (6.42 ± 0.37) × 10⁵ M⁻¹; ΔH₁ = −10.57 ± 0.83 kcal mol⁻¹; −TΔS₁ = 2.64 ± 0.83 kcal mol⁻¹; Kₐ₂ = (9.49 ± 0.23) × 10⁵ M⁻¹; ΔH₂ = −11.47 ± 1.04 kcal mol⁻¹; −TΔS₂ = 3.31 ± 1.04 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (6.09 ± 0.38) × 10¹¹ M⁻²; ΔH = −22.14 ± 1.33 kcal mol⁻¹; −TΔS = 5.95 ± 1.33 kcal mol⁻¹
Bipip, direct titration	Kₐ₁ = (1.11 ± 0.01) × 10⁶ M⁻¹; ΔH₁ = −5.23 ± 0.02 kcal mol⁻¹; −TΔS₁ = −3.01 ± 0.02 kcal mol⁻¹; Kₐ₂ = (2.09 ± 0.02) × 10⁵ M⁻¹; ΔH₂ = −7.64 ± 0.14 kcal mol⁻¹; −TΔS₂ = 0.39 ± 0.14 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (2.31 ± 0.03) × 10¹¹ M⁻²; ΔH = −12.87 ± 0.14 kcal mol⁻¹; −TΔS = −2.62 ± 0.14 kcal mol⁻¹
Me4Bipip, direct titration	Kₐ₁ = (1.28 ± 0.11) × 10⁶ M⁻¹; ΔH₁ = −12.33 ± 1.15 kcal mol⁻¹; −TΔS₁ = 4.00 ± 1.15 kcal mol⁻¹; Kₐ₂ = (6.48 ± 0.31) × 10⁵ M⁻¹; ΔH₂ = −12.63 ± 1.42 kcal mol⁻¹; −TΔS₂ = 4.70 ± 1.42 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (8.29 ± 0.82) × 10¹¹ M⁻²; ΔH = −24.96 ± 1.83 kcal mol⁻¹; −TΔS = 8.70 ± 1.83 kcal mol⁻¹
PPCP, direct titration	Kₐ₁ = (1.02 ± 0.08) × 10⁶ M⁻¹; ΔH₁ = −9.08 ± 0.82 kcal mol⁻¹; −TΔS₁ = 0.88 ± 0.82 kcal mol⁻¹; Kₐ₂ = (1.04 ± 0.13) × 10⁵ M⁻¹; ΔH₂ = −15.77 ± 0.69 kcal mol⁻¹; −TΔS₂ = 8.92 ± 0.69 kcal mol⁻¹; Kₐ₁·Kₐ₂ = (1.06 ± 0.16) × 10¹¹ M⁻²; ΔH = −24.85 ± 1.07 kcal mol⁻¹; −TΔS = 9.80 ± 1.07 kcal mol⁻¹
ITC thermograms and fitted curves	Image data were not transcribed