Compound characterization data — Brunner et al., 2026

Kyle Brunner, Yanfeng Fan, Chongsong Xu, Owen O’Sullivan, Melody Pham, Michael J. Zdilla, Christian E. Schafmeister. “The design and application of diureido functionalized spiroligomers as diphosphate receptors.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007885/v1

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Receptor 5a with H₂PPi
¹H NMR titration (CD₃CN/DMSO-d₆ = 9:1), apparent association constant	899.2 ± 162.8 M⁻¹

Receptor 5b with H₂PPi
¹H NMR titration, apparent association constant	155 M⁻¹
¹H NMR titration, NH signals	Broadened at first and reappeared after the addition of approximately 1 equiv of H₂PPi

Receptor 5c with H₂PPi
¹H NMR titration, NH signals	Broadened at first and reappeared after the addition of approximately 1 equiv of H₂PPi; overlapping NH signals complicated the analysis and prevented reliable fitting of a binding constant

Receptors 5a–5f with HPPi
¹H NMR titration (CD₃CN/DMSO-d₆ 9:1 and D₂O/DMSO-d₆ 2:98)	Urea hydrogens were deprotonated

Anion receptors 5a–5e
¹H NMR titration binding constants	Image data were not transcribed

3a
¹H NMR (500 MHz, DMSO-d₆, rt)	δ 9.15 (s, 1H), 8.06–7.96 (m, 2H), 7.57 (s, 1H), 7.22 (s, 1H), 4.20–4.11 (m, 1H), 3.71 (d, J = 11.2 Hz, 1H), 3.61 (d, J = 11.4 Hz, 1H), 3.55–3.41 (m, 2H), 3.30 (t, J = 7.1 Hz, 2H), 3.14 (dd, J = 13.5, 9.3 Hz, 1H), 2.38–2.27 (m, 1H), 1.90–1.78 (m, 2H), 1.76–1.58 (m, 2H), 1.36 (s, 9H), 1.35 (s, 9H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 171.8, 168.0, 153.9, 142.4, 131.1 (q, J = 32.4 Hz), 123.7 (q, J = 272.6 Hz), 117.8, 114.4, 81.1, 79.6, 63.0, 58.5, 54.6, 47.8, 47.2, 39.0, 28.3, 27.9, 27.0, 23.2
HRMS (ESI)	m/z calculated for C₂₈H₃₆F₆N₄O₆+H⁺: 639.2612 [M+H]⁺, found 639.2617

3b
¹H NMR (500 MHz, DMSO-d₆, 350 K)	δ ¹H NMR (500 MHz, DMSO-d₆, 350 K, δ) 8.89 (s, 1H), 8.01 (s, 2H), 7.51 (s, 1H), 7.22 (s, 1H), 4.19 (s, 1H), 3.90 (d, J = 11.3 Hz, 1H), 3.66 (s, 1H), 3.41 (s, 4H), 3.06 (s, 1H), 2.68 (s, 1H), 1.77 (s, 4H), 1.43 (s, 9H), 1.39 (s, 9H)
¹³C NMR (126 MHz, DMSO-d₆, 350 K)	δ 170.9, 167.0, 153.5, 142.1, 130.9 (q, J = 32.6 Hz), 123.3 (q, J = 272.8 Hz), 117.8, 117.8, 114.0, 80.7, 79.3, 63.6, 58.3, 54.3, 46.9, 38.7, 28.1, 27.7, 22.9
HRMS (ESI)	m/z calculated for C₂₈H₃₆F₆N₄O₆+H⁺: 639.2612 [M+H]⁺, found 639.2639

3c
¹H NMR (500 MHz, DMSO-d₆, 350 K)	δ 9.12 (s, 1H), 7.99 (s, 2H), 7.50 (s, 1H), 7.10 (s, 1H), 4.17 (dd, J = 9.2, 4.9 Hz, 1H), 3.87 (s, 1H), 3.53 (s, 1H), 3.40 (s, 4H), 3.10 (s, 1H), 2.29 (dd, J = 13.4, 4.9 Hz, 1H), 1.78 (s, 4H), 1.39 (s, 9H), 1.37 (s, 9H)
¹³C NMR (126 MHz, DMSO-d₆, 350 K)	δ 171.2, 167.7, 153.4, 153.1, 142.0, 130.9 (q, J = 32.7 Hz), 123.3 (q, J = 273.0 Hz), 117.7, 113.9, 80.7, 79.3, 63.2, 58.4, 54.8, 46.9, 38.5, 28.0, 27.6, 24.3
HRMS (ESI)	m/z calculated for C₂₈H₃₆F₆N₄O₆+H⁺: 639.2612 [M+H]⁺, found 639.2608

3d
¹H NMR (500 MHz, DMSO-d₆, TFA added, rt)	δ 8.44 (s, 1H), 7.31 (d, J = 8.3 Hz, 2H), 7.19 (t, J = 7.9 Hz, 2H), 6.90 (s, 1H), 6.88 (t, J = 7.3 Hz, 1H), 4.15 (dd, J = 9.2, 4.1 Hz, 1H), 3.67 (d, J = 11.3 Hz, 1H), 3.56–3.34 (m, 3H), 3.29 (t, J = 7.1 Hz, 2H), 3.10 (dd, J = 13.4, 9.4 Hz, 1H), 2.37–2.26 (m, 1H), 1.88–1.57 (m, 4H), 1.42–1.30 (m, 18H)
¹³C NMR (126 MHz, DMSO-d₆, TFA added, rt)	δ 171.8, 168.4, 154.0, 153.4, 140.4, 129.1, 121.8, 118.0, 81.1, 79.6, 62.8, 58.5, 54.9, 47.1, 38.1, 28.3, 27.9, 23.2
HRMS (ESI)	m/z calculated for C₂₈H₃₆F₆N₄O₆+H⁺: 639.2612 [M+H]⁺, found 503.2878

3e
¹H NMR (500 MHz, DMSO-d₆, 1 % TFA, 345 K)	δ 8.69 (s, 1H), δ 7.84 (s, 1H), 7.51–7.34 (m, 2H), 7.21 (d, J = 7.2 Hz, 1H), 6.89 (s, 1H), 4.16 (dd, J = 9.2, 4.7 Hz, 1H), 3.84 (s, 1H), 3.52 (s, 1H) 3.40 (s, 4H), 3.09 (s, 1H), 2.28 (dd, J = 13.4, 4.6 Hz, 1H), 1.77 (s, 4H), 1.39 (s, 9H)
¹³C NMR (126 MHz, DMSO-d₆, 345 K)	δ 171.2, 167.9, 153.6, 153.1, 140.8, 129.7 (q, J = 31.4 Hz), 123.6 (q, J = 272.3 Hz) 121.4, 117.7, 113.9, 80.6, 79.2, 62.9, 58.4, 54.8, 46.9, 38.8, 28.0, 27.6, 24.5
HRMS (ESI)	m/z calculated for C₂₇H₃₇F₃N₄O₆+H⁺: 571.2738 [M+H]⁺, found 571.2764

4a
¹H NMR (500 MHz, DMSO-d₆, 1 % TFA added, rt)	δ 10.26 (s, 1H), 9.85 (s, 1H), 9.06 (s, 1H), 8.47 (s, 1H), 8.06 (s, 2H), 7.56 (s, 1H), 4.31 (t, J = 8.4 Hz, 1H), 4.19 (d, J = 11.6 Hz, 1H), 3.61–3.57 (m, 1H), 3.41 (d, J = 11.6 Hz, 1H), 3.33 (dd, J = 8.1, 5.9 Hz, 2H), 3.30–3.26 (m, 1H), 2.77 (dd, J = 13.5, 8.3 Hz, 1H), 2.48–2.45 (m, 1H), 1.85–1.81 (m, 2H), 1.78–1.73 (m, J = 10.9, 5.3 Hz, 1H), 1.63–1.59 (m, 1H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 172.1, 167.6, 154.3, 143.0, 130.3 (q, J = 32.1 Hz), 123.3 (q, J = 272.7 Hz), 116.6, 112.8, 64.0, 59.5, 52.2, 47.4, 46.6, 36.3, 26.6, 22.7
HRMS (ESI)	m/z calculated for C₁₉H₂₀F₆N₄O₄+Na⁺: 505.1281 [M+Na]⁺, found 505.1267

4b
¹H NMR (500 MHz, DMSO-d₆, 1 % TFA added, 345 K)	δ 9.60 (s, 1H), 8.05 (s, 2H), 7.94 (s, 1H), 7.54 (s, 1H), 4.59 (t, J = 8.5 Hz, 1H), 4.19 (d, J = 12.1 Hz, 1H), 3.60 (d, J = 12.0 Hz, 1H), 3.40 (s, 4H), 2.76 (dd, J = 13.8, 8.4 Hz, 1H), 2.52 (dd, J = 13.8, 8.5 Hz, 1H), 1.81 (s, 4H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 170.5, 167.1, 154.0, 142.3, 130.7 (q, J = 32.6 Hz), 123.3 (q, J = 272.6 Hz), 117.3, 113.9, 64.3, 59.1, 53.5, 47.5, 46.7, 36.6, 26.5, 22.7
HRMS (ESI)	m/z calculated for C₁₉H₂₀F₆N₄O₄+Na⁺: 505.1281 [M+Na]⁺, found 505.1282

4c
¹H NMR (500 MHz, DMSO-d₆, 1 % TFA added, rt)	δ 10.26 (s, 1H), 9.89 (s, 1H), 9.09 (s, 1H), 8.48 (s, 1H), 8.09 (d, J = 1.5 Hz, 2H), 7.59 (s, 1H), 4.34 (t, J = 9.1 Hz, 1H), 4.22 (d, J = 11.7 Hz, 1H), 3.65–3.57 (m, 1H), 3.44 (d, J = 11.7 Hz, 1H), 4.34 (t, J = 9.1 Hz, 1H), 4.22 (d, J = 11.7 Hz, 1H), 3.65–3.57 (m, 1H), 3.36 (dd, J = 8.5, 5.6 Hz, 2H), 3.33–3.28 (m, 1H), 2.80 (dd, J = 13.5, 8.3 Hz, 1H), 2.51–2.46 (m, 1H), 1.92–1.81 (m, 2H), 1.81–1.74 (m, 1H), 1.67–1.58 (m, 1H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 172.7, 168.1, 154.7, 143.5, 130.7 (q, J = 32.2 Hz), 123.8 (q, J = 272.5 Hz), 117.0, 113.2, 64.5, 60.0, 52.7, 47.9, 36.8, 27.1, 23.2
HRMS (ESI)	m/z calculated for C₁₉H₂₀F₆N₄O₄+H⁺: 483.1462 [M+H]⁺, found 483.1440

4d
¹H NMR (500 MHz, DMSO-d₆, 1 % TFA added, rt)	δ 9.83 (s, 1H), 9.08 (s, 1H), 9.04 (s, 1H), 7.75 (s, 1H), 7.42–7.33 (m, 2H), 7.23 (dd, J = 8.6, 7.3 Hz, 2H), 6.92 (t, J = 7.3 Hz, 1H), 4.34 (s, 1H), 4.18 (d, J = 11.7 Hz, 1H), 3.69–3.58 (m, 1H), 3.39 (d, J = 11.7 Hz, 1H), 3.36–3.28 (m, 3H), 2.75 (dd, J = 13.5, 8.5 Hz, 1H), 2.43 (dd, J = 13.6, 9.4 Hz, 1H), 1.95–1.73 (m, 3H), 1.70–1.55 (m, 1H)
¹³C NMR (126 MHz, DMSO-d₆, 1 % TFA added, rt)	δ 169.8, 168.6, 154.5, 140.3, 129.1, 122.0, 118.3, 63.8, 58.0, 54.5, 48.0, 47.2, 36.6, 26.9, 23.2
HRMS (ESI)	m/z calculated for C₁₇H₂₃N₄O₄+H⁺: 347.1714 [M+H]⁺, found 347.1727

4e
¹H NMR (500 MHz, DMSO-d₆, rt)	δ 11.32 (s, 1H), 9.39 (s, 1H), 8.02 (s, 1H), 7.63 (d, J = 8.4 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.16 (d, J = 7.7 Hz, 1H), 4.17 (d, J = 12.8 Hz, 1H), 4.00 (d, J = 11.8 Hz, 1H) 3.88 (d, J = 12.0 Hz, 1H), 3.87–3.80 (m, 1H) 3.34–3.27 (m, 3H), 2.98 (d, J = 13.1 Hz, 1H), 2.28 (t, J = 12.2 Hz, 1H), 1.89–1.69 (m, 3H) 1.64–1.52 (m, 1H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 172.1, 168.7, 155.3, 142.3, 129.9, 129.8 (q, J = 31.4 Hz), 124.8 (q, J = 274.5 Hz), 121.5, 117.4, 113.8, 64.4, 59.9, 53.7, 47.9, 47.1, 36.6, 27.2, 23.2
HRMS (ESI)	m/z calculated for C₁₈H₂₁F₃N₄O₄+H⁺: 415.1588 [M+H]⁺, found 415.1578

6
¹H NMR (500 MHz, DMSO-d₆, 345 K)	δ 9.14 (s, 1H), 8.00 (s, 2H), 7.49 (s, 1H), 7.21 (s, 1H), 5.89 (s, 1H), 5.29 (d, J = 17.3 Hz, 1H), 5.17 (d, J = 10.3 Hz, 1H), 4.53 (m, 2H), 4.28 (s, 1H), 4.17 (s, 1H), 3.55 (d, J = 11.0 Hz, 1H), 3.41 (s, 4H), 3.05 (s, 1H), 2.29 (dd, J = 13.3, 5.8 Hz, 1H), 1.77 (s, 4H)
¹³C NMR (126 MHz, DMSO-d₆, 345 K)	δ 173.1, 167.8, 153.7, 153.6, 142.1, 133.2, 130.9 (q, J = 32.7 Hz), 123.3 (q, J = 272.8 Hz), 117.7, 116.7, 113.9, 65.1, 63.1, 58.0, 55.2, 47.0, 38.8, 24.9
HRMS (ESI)	m/z calculated for C₂₃H₂₅F₆N₄O₆+H⁺: 567.1673 [M+H]⁺, found 567.1667

5a
¹H NMR (500 MHz, Methanol-d₄, rt)	δ 7.78 (s, 4H), 7.38 (s, 2H), 4.63 (dd, J = 8.5, 5.4 Hz, 2H), 4.38 (d, J = 12.2 Hz, 2H), 4.14 (d, J = 12.2 Hz, 2H), 3.85–3.70 (m, 2H), 3.54–3.41 (m, 4H), 3.43–3.35 (m, 2H), 2.81 (dd, J = 13.6, 5.7 Hz, 2H), 2.67 (dd, J = 13.5, 8.8 Hz, 2H), 2.01–1.88 (m, 4H), 1.91–1.82 (m, 2H), 1.76–1.66 (m, 2H)
¹³C NMR (126 MHz, CD₃CN/DMSO-d₆ = 1.3/1, 320 K)	δ 167.2, 165.4, 153.1, 141.1, 130.0 (q, J = 33.0 Hz), 122.5 (q, J = 272.1 Hz), 116.8, 113.4, 62.2, 57.4, 53.0, 46.5, 45.9, 34.2, 25.7, 21.9
HRMS (ESI)	m/z calculated for C₃₈H₃₇F₁₂N₈O₆+H⁺: 929.2639 [M+H]⁺, found 929.2623

5b
¹H NMR (500 MHz, CD₃CN/DMSO-d₆ = 9/1, rt)	δ 9.01 (s, 2H), 7.99 (s, 4H), 7.50 (s, 2H), 7.44 (s, 2H), 4.54 (t, J = 8.4 Hz, 2H), 4.15 (d, J = 12.4 Hz, 2H), 3.68 (d, J = 12.3 Hz, 2H), 3.56 (s, 2H), 3.47 (s, 2H), 3.35 (s, 4H), 2.63–2.60 (m, 2H), 2.46–2.44 (m, 2H), 1.91–1.80 (m, 8H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 167.7, 165.6, 154.0, 142.7, 130.6 (q, J = 32.5 Hz), 123.4 (q, J = 272.7 Hz), 117.2, 113.4, 62.6, 58.5, 53.8, 47.5, 46.7, 35.7, 26.6, 22.7
HRMS (ESI)	m/z calculated for C₃₈H₃₇F₁₂N₈O₆+H⁺: 929.2639 [M+H]⁺, found 929.2617

5c
¹H NMR (500 MHz, CD₃CN/DMSO-d₆ = 9/1, rt)	δ 9.41 (s, 1H), 9.34 (s, 1H), 8.01 (s, 2H), 7.99 (s, 2H), 7.93 (s, 1H), 7.67 (s, 1H), 7.49 (s, 2H), 4.79 (d, J = 12.6 Hz, 1H), 4.49 (dd, J = 11.7, 5.8 Hz, 1H), 4.24–4.17 (m, 1H), 4.13 (d, J = 12.4 Hz, 1H), 4.04 (d, J = 12.4 Hz, 1H), 3.61–3.50 (m, 2H), 3.46 (q, J = 7.6 Hz, 1H), 3.43–3.31 (m, 6H), 2.81–2.71 (m, 1H), 2.47–2.37 (m, 2H), 2.23 (dd, J = 12.7, 10.8 Hz, 1H), 1.85–1.60 (m, 8H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 169.3, 168.8, 168.2, 163.6, 162.9, 154.5, 154.5, 142.9, 142.9, 131.1 (q, J = 32.7 Hz), 131.1 (q, J = 32.7 Hz), 123.8 (q, J = 272.7 Hz), 123.8 (q, J = 272.7 Hz), 117.9, 117.8, 114.2, 62.9, 62.5, 59.2, 58.7, 55.3, 48.0, 48.0, 47.3, 47.2, 46.4, 46.3, 27.0, 26.9, 26.4, 26.4, 23.3
HRMS (ESI)	m/z calculated for C₃₈H₃₇F₁₂N₈O₆+H⁺: 929.2639 [M+H]⁺, found 929.2600

5d
¹H NMR (500 MHz, DMSO-d₆, rt)	δ 8.58 (s, 2H), 7.22 (d, J = 8.0 Hz, 4H), 7.12 (t, J = 7.8 Hz, 4H), 6.87 (s, 2H), 6.83 (t, J = 7.3 Hz, 2H), 4.38 (t, J = 7.8 Hz, 2H), 4.06 (d, J = 11.9 Hz, 2H), 3.74 (d, J = 11.9 Hz, 2H), 3.51 (s, 2H), 3.25–3.23 (m, 2H), 2.54 (dd, J = 13.4, 8.8 Hz, 2H), 2.49–2.40 (m, 6H), 1.84–1.73 (m, 4H), 1.72–1.62 (m, 2H), 1.61–1.49 (m, 2H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 168.96, 165.77, 154.38, 140.40, 129.13, 121.83, 118.11, 62.49, 58.30, 54.58, 47.85, 47.13, 36.20, 27.00, 23.21
HRMS (ESI)	m/z calculated for C₃₄H₄₁N₈O₆+H⁺: 657.3144 [M+H]⁺, found 657.3148

5e
¹H NMR (500 MHz, CD₃CN/DMSO-d₆ = 9/1, rt)	δ 9.16 (s, 1H), 8.92 (s, 1H), 8.00 (s, 2H), 7.93 (s, 2H), 7.58 (s, 1H), 7.52 (s, 1H), 7.50 (s, 1H), 6.20 (s, 1H), 4.73 (d, J = 11.4 Hz, 1H), 4.52 (dd, J = 8.7, 3.8 Hz, 1H), 4.39 (dd, J = 9.3, 2.7 Hz, 1H), 3.98 (dd, J = 11.7, 2.2 Hz, 1H), 3.79–3.72 (m, 1H), 3.58–3.51 (m, 2H), 3.48–3.40 (m, 3H), 3.39–3.33 (m, 2H), 3.32–3.25 (m, 1H), 3.19 (d, J = 11.4 Hz, 1H), 3.04–2.96 (m, 2H), 2.88–2.74 (m, 2H), 1.89–1.65 (m, 8H)
¹³C NMR (126 MHz, DMSO-d₆ rt)	δ 168.0, 167.7, 165.7, 165.6, 153.8, 142.2, 142.1, 130.7 (q, J = 32.7 Hz), 130.7 (q, J = 32.7 Hz), 124.9 (q, J = 272.1 Hz), 124.9 (q, J = 272.1 Hz), 117.5, 117.3, 113.9, 113.9, 62.3, 62.1, 58.0, 57.7, 54.2, 53.6, 47.6, 47.4, 46.8, 35.5, 35.3, 26.5, 22.7, 22.6
HRMS (ESI)	m/z calculated for C₃₈H₃₇F₁₂N₈O₆+H⁺: 929.2639 [M+H]⁺, found 929.2600

5f
¹H NMR (500 MHz, DMSO-d₈, rt)	δ 8.96 (s, 2H), 7.87 (s, 2H), 7.33 (t, J = 7.9, Hz, 2H), 7.24–7.18 (m, 4H) 6.80 (s, 2H), 4.49 (t, J = 7.5 Hz, 2H), 4.12 (d, J = 11.9 Hz, 2H), 3.91 (d, J = 11.9 Hz, 2H), 3.57 (dd, J = 10.4, 5.3 Hz 2H), 3.34–3.31 (m, 4H), 3.30 (s, 2H), 2.60–2.55 (m, 4H), 1.89–1.80 (m, 4H), 1.75–1.69 (m, 2H), 1.63–1.57 (m, 2H)
¹³C NMR (126 MHz, DMSO-d₆, rt)	δ 168.16, 165.46, 153.84, 140.71, 129.67, 129.34 (q, J = 31.5 Hz), 124.19 (q, J = 272.4 Hz), 121.17, 117.59, 113.47, 62.20, 57.84, 53.92, 47.36, 46.63, 35.41, 26.48, 22.70
HRMS (ESI)	m/z calculated for C₃₆H₃₈F₆N₈O₆+H⁺: 793.2891 [M+H]⁺, found 793.2860

Compounds 3a, 5a, 5b, 5c, 5e and 5f
Single-crystal XRD structures	Image data were not transcribed
Single-crystal XRD, 5a	The two urea groups point to the same face of the 5-6-5 fused ring system and create a pocket with the spiroligomer backbone
Single-crystal XRD, 5e	The two urea arms are positioned on opposite faces of the fused ring system
Single-crystal XRD, 5b and 5c	The urea groups are positioned on the same face of the fused ring system, but too far apart to form a binding pocket to coordinate to an anion
Single-crystal XRD, 5f	Observed in complex with a disordered phosphate