Compound characterization data

Jiarui Su, Huiyu Liu, Yongji Gong, Muyu Lu, Zezhao Xu, Muyao Yu, Guanzhi Wang, Weiwei Zhang, Lin Xiong, Na Yu, Qisheng Wang, Linjiang Chen, Wei Li, Wei-Hong Zhu, Shan Jiang. “Counteranion-directed polar packing in organic cage piezoelectrics.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007897/v1

CC3
¹H NMR (400 MHz, CDCl₃)	δ 8.15 (s, 12H, -ArH), 7.89 (s, 12H, -ArCH), 3.34 (s, 12H, -NCH), 1.83 (d, J = 8.7 Hz, 12H, CH₂), 1.67 (s, 12H, CH₂), 1.47 (d, J = 9.8 Hz, 12H, CH₂), 1.26 (d, J = 4.0 Hz, 12H, CH₂)

CC19
¹H NMR (400 MHz, CDCl₃)	δ 8.60 (s, 4H, -ArH), 8.26 (s, 4H, -ArH), 8.06 (s, 4H, -ArCH), 7.83 (s, 8H, -ArCH), 3.32 (s, 12H, -NCH), 1.82 (s, 26H, CH₂), 1.56–0.79 (m, 22H, CH₂)

RCC3
¹H NMR (400 MHz, CDCl₃)	δ 7.11 (s, 12H, -ArH), 3.82 (d, J = 14.0 Hz, 12H, -ArCH₂), 3.56 (d, J = 14.1 Hz, 12H, -ArCH₂), 2.21–0.93 (m, 60H, -NCH, CH₂)

RCC19
¹H NMR (400 MHz, CDCl₃)	δ 7.18–6.48 (m, 8H, -ArH), 4.22–3.17 (m, 24H, -ArCH₂), 2.38–0.93 (m, 60H, -NCH, CH₂)

RCC3-Br
¹H NMR (400 MHz, D₂O)	δ 7.42 (s, 12H, -ArH), 4.07 (d, J = 13.6 Hz, 12H, -ArCH₂), 3.89 (d, J = 13.6 Hz, 12H, -ArCH₂), 2.97 (s, 12H, -NCH), 2.10 (d, J = 12.3 Hz, 12H, CH₂), 1.78–1.70 (m, 12H, CH₂), 1.44–1.27 (m, 24H, CH₂)
Powder XRD, Rietveld refinement (300 K)	Rwp = 8.40 %; Rp = 6.38 %; a = 15.7242 Å; b = 24.0046 Å; c = 26.7959 Å; space group P2₁2₁2₁; image data were not transcribed

RCC3-SO₄
¹H NMR (400 MHz, D₂O)	δ 7.45 (s, 12H, -ArH), 4.47 (d, J = 13.2 Hz, 12H, -ArCH₂), 3.78 (d, J = 13.1 Hz, 12H, -ArCH₂), 3.67–3.58 (m, 12H, -NCH), 2.38 (d, J = 12.2 Hz, 12H, CH₂), 1.83 (d, J = 8.9 Hz, 12H, CH₂), 1.52–1.41 (m, 12H, CH₂), 1.31 (d, J = 10.7 Hz, 12H, CH₂)
Powder XRD, Rietveld refinement (300 K)	Rwp = 5.76 %; Rp = 4.21 %; a = 40.7203 Å; b = 26.0586 Å; c = 29.5649 Å; space group R3; image data were not transcribed

RCC3-CF₃SO₃
¹H NMR (400 MHz, 298 K, D₂O)	δ 7.60 (s, 12H, -ArH), 4.40 (d, 12H, -ArCH₂), 4.21 (d, 12H, -ArCH₂), 3.74–3.59 (m, 12H, -NCH), 2.18–1.55 (m, 48H, CH₂)
Single-crystal XRD (100 K)	Formula weight: 2974.67 g/mol; chemical formula: C₈₅H₁₂₄F₃₆N₁₂O₃₇S₁₂; crystal system: Tetragonal; space group: P4₁; Z: 4; a = 25.9930(8) Å; b = 25.9930(8) Å; c = 28.3881(13) Å; α = 90°; β = 90°; γ = 90°; volume: 19180.0(12) Å³; ρcalc: 1.030 g cm⁻³; μ: 0.22 mm⁻¹; F(000): 6120.0; 2θ range: 4.51 to 50.97° (0.80 Å); data/restraints/parameters: 253947/19/648; goodness-of-fit on F²: 1.058; total reflections: 253947; unique reflections: 39237; Rint: 0.0362; R1: 0.1260; wR2: 0.3340; largest peak/hole: 1.22/−0.77 e Å⁻³
Powder XRD, Rietveld refinement (150 K)	Rwp = 10.90 %; Rp = 8.00 %; a = 26.0332 Å; b = 26.0332 Å; c = 28.4187 Å; space group P4₁; image data were not transcribed
Variable-temperature synchrotron PXRD	Powder remained crystalline and structurally unchanged at 375 K; image data were not transcribed
TGA (30–500 °C, 10 °C min⁻¹, N₂)	Thermal stability up to 200 °C; weight loss (~6 %) before decomposition was tentatively attributed to the removal of volatile solvent; image data were not transcribed

RCC19-Br
¹H NMR (400 MHz, D₂O)	δ 7.55–7.14 (m, 8H, -ArH), 4.53–3.66 (m, 24H, -ArCH₂), 3.50–2.79 (m, 12H, -NCH), 2.38–2.07 (m, 8H, CH₂), 1.85–1.18 (m, 40H, CH₂)
Single-crystal XRD (100 K)	Formula weight: 2176.68 g/mol; chemical formula: C₇₂H₁₂₀Br₁₂N₁₂O₄; crystal system: Hexagonal; space group: P6₃; Z: 6; a = 14.7908(11) Å; b = 14.7908(11) Å; c = 56.462(6) Å; α = 90°; β = 90°; γ = 120°; volume: 10697.2(16) Å³; ρcalc: 1.350 g cm⁻³; μ: 4.53 mm⁻¹; F(000): 4344.0; 2θ range: 4.64 to 44.96° (0.90 Å); data/restraints/parameters: 235017/68/287; goodness-of-fit on F²: 1.0730; total reflections: 235017; unique reflections: 10281; Rint: 0.1023; R1: 0.1570; wR2: 0.3981; largest peak/hole: 0.97/−1.24 e Å⁻³
Powder XRD, Rietveld refinement (150 K)	Rwp = 3.91 %; Rp = 2.81 %; a = 14.9644 Å; b = 14.9644 Å; c = 57.2342 Å; space group P6₃; image data were not transcribed
Single-crystal XRD, crystal packing	Br⁻ anions are accommodated within the cage windows and stabilized by O–H···Br and N–H···Br hydrogen-bonding interactions with the protonated cage framework; image data were not transcribed
Variable-temperature synchrotron PXRD	Powder remained crystalline and structurally unchanged at 355 K; image data were not transcribed
TGA (30–500 °C, 10 °C min⁻¹, N₂)	Thermal stability up to 200 °C; weight loss (~8 %) before decomposition was tentatively attributed to the removal of volatile solvent; image data were not transcribed

RCC19-SO₄
¹H NMR (400 MHz, D₂O)	δ 7.67–7.44 (m, 8H, -ArH), 4.59–4.19 (m, 18H, -ArCH₂), 3.96–3.83 (m, 6H, -ArCH₂), 3.82–3.48 (m, 12H, -NCH), 2.44 (s, 12H, CH₂), 1.88 (d, J = 11.9 Hz, 12H, CH₂), 1.61 (d, J = 11.4 Hz, 12H, CH₂), 1.42 (d, J = 14.4 Hz, 12H, CH₂)
Single-crystal XRD (100 K)	Formula weight: 1794.17 g/mol; chemical formula: C₇₂H₁₂₀N₁₂O₂₈S₆; crystal system: Hexagonal; space group: R3; Z: 9; a = 24.8278(15) Å; b = 24.8278(15) Å; c = 41.717(4) Å; α = 90°; β = 90°; γ = 120°; volume: 22270.0(3) Å³; ρcalc: 0.802 g cm⁻³; μ: 0.14 mm⁻¹; F(000): 5724.0; 2θ range: 4.94 to 49.08° (0.90 Å); data/restraints/parameters: 72863/24/298; goodness-of-fit on F²: 1.1350; total reflections: 72863; unique reflections: 18072; Rint: 0.0623; R1: 0.1189; wR2: 0.3213; largest peak/hole: 1.81/−0.73 e Å⁻³
Powder XRD, Rietveld refinement (150 K)	Rwp = 7.11 %; Rp = 5.16 %; a = 25.0280 Å; b = 25.0280 Å; c = 42.4854 Å; space group R3; image data were not transcribed
Variable-temperature synchrotron PXRD	Powder remained crystalline and structurally unchanged at 340 K; image data were not transcribed
TGA (30–500 °C, 10 °C min⁻¹, N₂)	Thermal stability up to 200 °C; weight loss (~35 %) before decomposition was tentatively attributed to the removal of volatile solvent; image data were not transcribed

RCC19-CF₃SO₃
¹H NMR (400 MHz, D₂O)	δ 7.42–7.24 (m, 8H, -ArH), 4.52–3.85 (m, 24H, -ArCH₂), 3.36 (dd, J = 65.4, 26.8 Hz, 12H, -NCH), 2.11 (d, J = 52.9 Hz, 12H, CH₂), 1.55 (dd, J = 71.0, 36.2 Hz, 36H, CH₂)
Single-crystal XRD	Complete cage framework and two CF₃SO₃⁻ anions were located; the remaining ten CF₃SO₃⁻ anions could not be fully modelled
Powder XRD, Rietveld refinement (150 K)	Rwp = 8.13 %; Rp = 5.08 %; a = 26.3389 Å; b = 26.3389 Å; c = 28.8779 Å; space group I4₁; image data were not transcribed
Single-crystal XRD, crystal packing	Triflate anions form directional N–H···O hydrogen bonds with protonated cage sites, generating an anisotropic cage–anion interaction environment; image data were not transcribed
Variable-temperature synchrotron PXRD	Powder remained crystalline and structurally unchanged at 355 K; image data were not transcribed
TGA (30–500 °C, 10 °C min⁻¹, N₂)	Thermal stability up to 180 °C; weight loss (~10 %) before decomposition was tentatively attributed to the removal of volatile solvent; image data were not transcribed

RCC3-CF₃SO₃, RCC3-SO₄, RCC3-Br, RCC19-CF₃SO₃, RCC19-SO₄ and RCC19-Br
¹H and ¹³C NMR spectra (298 K, D₂O)	Image data were not transcribed

RCC3-CF₃SO₃/PDMS composite film
Radius	0.75 cm
Thickness	1.80 mm
Mass	290.4 mg
Sound velocity	0.898 mm/μs
Acoustic impedance	0.82 MRayl

RCC19-CF₃SO₃/PDMS composite film
Radius	0.75 cm
Thickness	1.75 mm
Mass	287.9 mg
Sound velocity	0.862 mm/μs
Acoustic impedance	0.78 MRayl

RCC3-CF₃SO₃, RCC19-Br, RCC19-CF₃SO₃ and RCC19-SO₄ single crystals
Optical microscopy and approximate crystal dimensions	Image data were not transcribed