Compound characterization data — Alba Martinez-Bascuñana et al., 2026

Alba Martinez-Bascuñana et al. “Zwitterionic dipnictanes as photoresponsive radical precursors.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007583/v1

Dimeric Sb(II) complex
Identifier	3-BF₄
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.60 (d, ³JH-H = 1.8 Hz, 4 H, H-3), 7.35 (d, ³JH-H = 7.5 Hz, 4 H, H-8), 7.07 (d, ³JH-H = 7.6 Hz, 4 H, H-8’), 6.95 (d, ³JH-H = 1.9 Hz, 4 H, H-4), 6.81 (d, ³JH-H = 7.8 Hz, 4 H, H-7), 6.76 (d, ³JH-H = 7.7 Hz, 4 H, H-7’), 2.36 (s, 6 H, H-10), 2.29 (s, 6 H, H-10’), 1.47 (s, 36 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 145.8 (C-6), 142.3 (C-6’), 138.4 (s, C-9 + C-9’), 138.3 (s, C-5), 135.6 (s, C-7’), 133.7 (s, C-7), 131.5 (s, C-8), 131.4 (s, C-4), 129.3 (s, C-8’), 124.1 (s, C-3), 61.8 (s, C-2), 32.2 (s, C-1), 21.2 (s, C-10), 21.1 (s, C-10’) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −151.8 (s, 4 F, BF₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: 2.45 (bs), −1.20 (s, BF₄) ppm
CHN	C₅₆H₇₂B₂F₈N₈Sb₂ calcd. C 51.90, H 5.60, N 8.65 %; exp. C 51.65, H 5.30, N 8.95 %

Dimeric Bi(II) complex
Identifier	4-BF₄
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.56 (d, ³JH-H = 2.0 Hz, 4 H, H-3), 7.37 (d, ³JH-H = 7.4 Hz, 4 H, H-8), 7.07 (d, ³JH-H = 7.5 Hz, 4 H, H-8’), 6.93 (d, ³JH-H = 2.0 Hz, 4 H, H-4), 6.71 – 6.68 (m, 8 H, H-7’ + H-7), 2.36 (s, 6 H, H-10), 2.30 (s, 6 H, H-10’), 1.44 (s, 36 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 152.9 (bs, C-5), 146.1 (bs, C-6’), 144.3 (bs, C-6), 138.8 (s, C-9 or C-9’), 138.2 (s, C-9 or C-9’), 135.6 (s, C-7’), 133.7 (s, C-7), 132.5 (s, C-8), f131.8 (s, C-4), 129.3 (s, C-8’), 123.8 (s, C-3), 60.9 (s, C-2), 32.3 (s, C-1), 21.2 (s, C-10), 21.1 (s, C-10’) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −151.8 (s, 4 F, BF₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: −1.20 (s, BF₄)
CHN	C₅₆H₆₉B₄Bi₂F₈N₈ calcd. C 45.81, H 4.81, N 7.63 %; exp. C 45.67, H 4.71, N 7.89 %
SC-XRD Bi–Bi bond length	3.085(1) Å
SC-XRD formula	C₆₂H₈₁B₄Bi₂F₈N₁₁
SC-XRD Dcalc (g cm⁻³)	1.609
SC-XRD μ (mm⁻¹)	5.402
SC-XRD formula weight	1593.653
SC-XRD crystal size (mm)	0.14×0.09×0.08
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	triclinic
SC-XRD space group	P−1
SC-XRD a (Å)	12.5026(1)
SC-XRD b (Å)	12.5425(1)
SC-XRD c (Å)	12.7457(1)
SC-XRD α (°)	112.241(1)
SC-XRD β (°)	92.029(1)
SC-XRD γ (°)	114.134(1)
SC-XRD V (Å³)	1644.95(3)
SC-XRD Z	1
SC-XRD Z′	0.5
SC-XRD wavelength (Å)	0.71073
SC-XRD radiation type	Mo Kα
SC-XRD Θmin (°)	1.77
SC-XRD Θmax (°)	45.28
SC-XRD index range h	−24 ≤ h ≤ 24
SC-XRD index range k	−25 ≤ k ≤ 25
SC-XRD index range l	−25 ≤ l ≤ 25
SC-XRD measured reflections	272411
SC-XRD independent reflections	27387
SC-XRD reflections I≥2σ(I)	24637
SC-XRD Rint	0.0678
SC-XRD parameters	404
SC-XRD restraints	59
SC-XRD largest peak (e Å⁻³)	2.6032
SC-XRD deepest hole (e Å⁻³)	−2.4988
SC-XRD GooF	1.0217
SC-XRD R1 (I≥2σ(I) / all)	0.0238 / 0.0298
SC-XRD wR2 (I≥2σ(I) / all)	0.0401 / 0.0412
SC-XRD CCDC deposition number	258915

Sb(II) complex
Identifier	3-BArF₂₄
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.73 – 7.69 (m, 16 H, H-12), 7.67 (bs, 8 H, H-14), 7.58 (d, ³JH-H = 1.8 Hz, 4 H, H-3), 7.34 (d, ³JH-H = 7.5 Hz, 4 H, H-8), 7.06 (d, ³JH-H = 7.4 Hz, 4 H, H-8’), 6.97 (d, ³JH-H = 1.9 Hz, 4 H, H-4), 6.82 (d, ³JH-H = 7.6 Hz, 4 H, H-7), 6.76 (d, ³JH-H = 7.8 Hz, 4 H, H-7’), 2.34 (s, 6 H, H-10), 2.27 (s, 6 H, H-10’), 1.46 (s, 36 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 162.6 (q, ¹JC-B = 49.8 Hz, BArF₂₄ C-11), 146.2 (C-6), 142.4 (C-6’), 138.6 (s, C-9), 138.5 (s, C-9’) 138.3 (s, C-5), 135.7 (s, BArF₂₄ C-12), 135.6 (s, C-7’), 133.7 (s, C-7), 131.5 (s, C-4), 131.4 (s, C-8), 129.9 (m, BArF₂₄ C-13), 129.4 (s, C-8’), 124.5 (q, ¹JC-F = 271.0 Hz, BArF₂₄ C-15), 124.0 (s, C-3), 118.6 (bs, BArF₂₄ C-14), 61.8 (s, C-2), 32.3 (s, C-1), 21.2 (s, C-10), 21.1 (s, C-10’) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −63.24 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: −1.19 (bs), −6.68 (bs, BArF₂₄) ppm
CHN	C₁₂₀H₉₃B₄F₄₈N₈Sb₂ calcd. C 50.65, H 3.29; N 3.94 %; exp. C 50.66, H 3.71, N 3.89 %
SC-XRD Sb–Sb bond length	2.995(1) Å
SC-XRD formula	C₁₂₅H₁₀₃.₅B₄F₄₈N₁₀.₅Sb₂
SC-XRD Dcalc (g cm⁻³)	1.512
SC-XRD μ (mm⁻¹)	4.381
SC-XRD formula weight	2951.525
SC-XRD crystal size (mm)	0.12×0.10×0.04
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	triclinic
SC-XRD space group	P−1
SC-XRD a (Å)	16.2120(4)
SC-XRD b (Å)	19.4444(5)
SC-XRD c (Å)	22.2039(4)
SC-XRD α (°)	90.104(2)
SC-XRD β (°)	99.569(2)
SC-XRD γ (°)	109.804(2)
SC-XRD V (Å³)	6481.0(3)
SC-XRD Z	2
SC-XRD Z′	1
SC-XRD wavelength (Å)	1.54184
SC-XRD radiation type	Cu Kα
SC-XRD Θmin (°)	2.42
SC-XRD Θmax (°)	66.60
SC-XRD index range h	−19 ≤ h ≤ 18
SC-XRD index range k	−23 ≤ k ≤ 23
SC-XRD index range l	−24 ≤ l ≤ 27
SC-XRD measured reflections	139132
SC-XRD independent reflections	22734
SC-XRD reflections I≥2σ(I)	14535
SC-XRD Rint	0.0708
SC-XRD parameters	1773
SC-XRD restraints	1778
SC-XRD largest peak (e Å⁻³)	1.6909
SC-XRD deepest hole (e Å⁻³)	−1.1641
SC-XRD GooF	1.0328
SC-XRD R1 (I≥2σ(I) / all)	0.0785 / 0.1170
SC-XRD wR2 (I≥2σ(I) / all)	0.2120 / 0.2416
SC-XRD CCDC deposition number	258913
Variable-concentration quantitative ¹H NMR (MeCN-d₃, 0.023–0.004 M; 1,3,5-trimethoxybenzene internal standard)	No change in the concentration of the dimeric Sb(II) complex 3-BArF₂₄ over the investigated concentration range, indicating that no detectable dissociation of the dimeric complex occurs upon dilution

Sb(II) complex
Identifier	3-OTf
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.59 (d, ³JH-H = 1.9 Hz, 4 H, H-3), 7.34 (d, ³JH-H = 7.5 Hz, 4 H, H-8), 7.07 (d, ³JH-H = 7.7 Hz, 4 H, H-8’), 6.95 (d, ³JH-H = 1.9 Hz, 4 H, H-4), 6.80 (d, ³JH-H = 7.5 Hz, 4 H, H-7), 6.75 (d, ³JH-H = 7.7 Hz, 4 H, H-7’), 2.36 (s, 6 H, H-10), 2.29 (s, 6 H, H-10’), 1.46 (s, 36 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 146.2 (C-6), 142.4 (C-6’), 138.5 (s, C-9), 138.4 (s, C-9’), 138.3 (s, C-5), 135.6 (s, C-7’), 133.7 (s, C-7), 131.5 (s, C-8), 131.4 (s, C-4), 129.3 (s, C-8’), 124.0 (s, C-3), 61.7 (s, C-2), 32.2 (s, C-1), 21.2 (s, C-10), 21.1 (s, C-10’) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −79.3 (s, 3 F, OTf) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: 2.28 (bs) ppm
CHN	C₅₈H₆₉B₂F₆N₈O₆S₂Sb₂ calcd. C 49.15, H 4.91, N 7.91 %; exp. C 49.67, H 4.73, N 7.77 %
UV–vis	λmax = 358 nm
SC-XRD Sb–Sb bond length	2.9324(1) Å
SC-XRD formula	C₅₈H₇₂B₂F₆N₈O₆S₂Sb₂
SC-XRD Dcalc (g cm⁻³)	1.519
SC-XRD μ (mm⁻¹)	1.009
SC-XRD formula weight	1420.559
SC-XRD crystal size (mm)	0.20×0.10×0.03
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	monoclinic
SC-XRD space group	I2/a
SC-XRD a (Å)	24.5516(3)
SC-XRD b (Å)	12.0475(1)
SC-XRD c (Å)	22.0385(2)
SC-XRD α (°)	90
SC-XRD β (°)	107.640(1)
SC-XRD γ (°)	90
SC-XRD V (Å³)	6212.15(11)
SC-XRD Z	4
SC-XRD Z′	0.5
SC-XRD wavelength (Å)	0.71073
SC-XRD radiation type	Mo Kα
SC-XRD Θmin (°)	2.18
SC-XRD Θmax (°)	45.01
SC-XRD index range h	−48 ≤ h ≤ 48
SC-XRD index range k	−23 ≤ k ≤ 23
SC-XRD index range l	−43 ≤ l ≤ 42
SC-XRD measured reflections	132400
SC-XRD independent reflections	25471
SC-XRD reflections I≥2σ(I)	21344
SC-XRD Rint	0.0507
SC-XRD parameters	412
SC-XRD restraints	1
SC-XRD largest peak (e Å⁻³)	1.4238
SC-XRD deepest hole (e Å⁻³)	−1.1771
SC-XRD GooF	1.0240
SC-XRD R1 (I≥2σ(I) / all)	0.0283 / 0.0391
SC-XRD wR2 (I≥2σ(I) / all)	0.0539 / 0.0573
SC-XRD CCDC deposition number	258914

Sb(III)-O and Sb(III)-OH complex mixture
Identifiers	6 and 6’
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.73 – 7.69 (m, H-12, BArF), 7.67 (bs, H-14, BArF), 7.60 (d, ³JH-H = 1.9 Hz, H-3 Sb(III)-OH 6’), 7.46 (d, ³JH-H = 1.8 Hz, H-3 Sb(III)-O 6), 7.19 (d, ³JH-H = 7.6 Hz, H-8 Sb(III)-O 6), 7.14 – 7.09 (m, H-8 + H-8’ Sb(III)-OH 6’), 7.07 – 7.03 (m, H-8’ Sb(III)-O 6 + H-4 Sb(III)-OH 6’), 6.81 (d, ³JH-H = 1.9 Hz, H-4 Sb(III)-O 6), 6.79 (bs, H-7 Sb(III)-OH 6’), 6.72 (d, ³JH-H = 7.7 Hz, H-7’ Sb(III)-O 6),6.65 – 6.60 (m, H-7 Sb(III)-O 6 + H-7’ Sb(III)-OH 6’),3.16 (bs, -OH Sb(III)-OH 6’), 2.31 (s, H-10 Sb(III)-O 6 + H-10 + H-10’ Sb(III)-OH 6’), 2.27 (s, H-10’ Sb(III)-O 6), 1.79 (s, H-1 Sb(III)-OH 6’), 1.55 (s, H-1 Sb(III)-O 6) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 162.6 (q, ¹JC-B = 49.8 Hz, BArF₂₄ C-11), 157.9 (s, C-5 Sb(III)-O 6), 156.0 (s, C-5 Sb(III)-OH 6’), 148.1 (s, C-6 Sb(III)-O 6) 146.5 (s, C-6’ Sb(III)-O 6), 138.6 (s, C-9 Sb(III)-OH 6’) 138.1 (s, C-9’ Sb(III)-OH 6’), 137.9 (s, C-9’ Sb(III)-O 6) 137.2 (s, C-9 Sb(III)-O 6), 135.7 (s, BArF₂₄ C-12), 135.4 (s, C-7’ Sb(III)-O 6), 134.7 (s, C-7’ Sb(III)-OH 6’) 134.0 (s, C-7 Sb(III)-OH 6’), 132.1 (s, C-7 Sb(III)-O 6), 130.0 (s, H-8 Sb(III)-O 6), 129.9 (m, BArF₂₄ C-13), 129.8 (s, H-8 + H-8’ Sb(III)-OH 6’), 129.3 (s, H-8’ Sb(III)-O 6), 128.7 (s, C-4 Sb(III)-OH 6’), 128.6 (s, C-4 Sb(III)-O 6), 124.5 (q, ¹JC-F = 271.0 Hz, BArF₂₄ C-15), 122.2 (s, C-3 Sb(III)-OH 6’), 121.4 (s, C-3 Sb(III)-O 6), 118.6 (bs, BArF₂₄ C-14), 61.8 (s, C-2 Sb(III)-OH 6’), 61.4 (s, C-2 Sb(III)-O 6) 32.8 (s, C-1 Sb(III)-O 6), 31.7 (s, C-1 Sb(III)-OH 6’), 21.2 (s, C-10 Sb(III)-O 6 + C-10 + C-10’ Sb(III)-OH 6’), 21.0 (s, C-10’ Sb(III)-O 6) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −63.2 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: 2.18 (bs), −6.67 (bs, BArF₂₄) ppm
¹H–¹³C{¹H} HMBC NMR	The NMR cross-peaks corresponding to the C-6 and C-6’ of the Sb(III)-OH 6’ complex could not be observed
HRMS (ASAP-pos, m/z)	calc’d for C₅₆H₇₆B₂N₈OSb₂²⁺ [M−2BArF₂₄]²⁺ 569.2042; found 569.2022

μ-oxo-bridged distibane
Identifier	6
SC-XRD Sb–O–Sb angle	180°
SC-XRD formula	C₁₂₄H₁₀₂B₄F₄₈N₁₀OSb₂
SC-XRD Dcalc (g cm⁻³)	1.542
SC-XRD μ (mm⁻¹)	0.549
SC-XRD formula weight	2946.998
SC-XRD crystal size (mm)	0.12×0.04×0.03
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	triclinic
SC-XRD space group	P−1
SC-XRD a (Å)	11.6628(1)
SC-XRD b (Å)	15.2508(1)
SC-XRD c (Å)	19.5641(2)
SC-XRD α (°)	105.330(1)
SC-XRD β (°)	104.231(1)
SC-XRD γ (°)	98.009(1)
SC-XRD V (Å³)	3174.36(6)
SC-XRD Z	1
SC-XRD Z′	0.5
SC-XRD wavelength (Å)	0.71073
SC-XRD radiation type	Mo Kα
SC-XRD Θmin (°)	1.85
SC-XRD Θmax (°)	38.21
SC-XRD index range h	−20 ≤ h ≤ 20
SC-XRD index range k	−26 ≤ k ≤ 26
SC-XRD index range l	−33 ≤ l ≤ 34
SC-XRD measured reflections	307363
SC-XRD independent reflections	33524
SC-XRD reflections I≥2σ(I)	27412
SC-XRD Rint	0.0837
SC-XRD parameters	955
SC-XRD restraints	1004
SC-XRD largest peak (e Å⁻³)	1.5854
SC-XRD deepest hole (e Å⁻³)	−1.1552
SC-XRD GooF	1.0326
SC-XRD R1 (I≥2σ(I) / all)	0.0432 / 0.0607
SC-XRD wR2 (I≥2σ(I) / all)	0.0900 / 0.0966
SC-XRD CCDC deposition number	258916

Sb(III) complex
Identifier	7
NMR assignment note	Significant broadening of several aromatic and aliphatic proton resonances was observed in both MeCN-d₃ and THF-d₈, thereby complicating the complete assignment of the corresponding ¹H and ¹³C NMR signals. Full characterization of complex 7 was performed in THF-d₈. Due to signal broadening and overlap, not all ¹H and ¹³C NMR resonances could be assigned unambiguously. Assignments are therefore provided only for those resonances that could be confidently identified. For signals that could not be assigned to a specific atom number, the corresponding carbon or proton environment (i.e., -CH Tol or -C Tol) is indicated where possible
¹H NMR (400 MHz, THF-d₈)	δ: 7.88 (d, ³JH-H = 1.9 Hz, 2 H, H-3), 7.80 – 7.76 (m, 8 H, H-17), 7.58 (bs, 4 H, H-19), 7.15 (d, ³JH-H = 8.1 Hz, 2 H, -CH Tol), 7.11 (d, ³JH-H = 1.9 Hz, 2 H, H-4), 7.08 (d, ³JH-H = 8.0 Hz, 2 H, H--CH Tol), 6.97 (bs, 4 H, -CH Tol), 6.39 (bs, 2 H, -CH Tol), 2.32 – 2.23 (m, 9 H, H-10 + H-10’ + H-15), 1.82 (s, 18 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, THF-d₈)	δ: 163.7 (q, ¹JC-B = 49.7 Hz, BArF₂₄ C-16), 148.0 (C-5), 139.6 (s, -C Tol), 136.0 (s, -CH Tol), 135.9 (s, -CH Tol), 135.9 (s, -CH Tol) 135.8 (s, BArF₂₄ C-17), 132.2 (s, -CH Tol), 131.2 (s, C-4), 129.9 (m, BArF₂₄ C-18), 129.9 (s, -CH Tol), 125.7 (q, ¹JC-F = 272.4 Hz, BArF₂₄ C-20), 122.9 (s, C-3), 118.4 (bs, BArF₂₄ C-19), 62.2 (s, C-2), 32.3 (s, C-1), 21.5 (s, C-10 + C-15), 21.1 (s, C-10’) ppm
¹⁹F{¹H} NMR (377 MHz, THF-d₈)	δ: −63.40 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, THF-d₈)	δ: 2.36 (bs), −6.50 (bs, BArF₂₄) ppm
HRMS (ASAP-pos, m/z)	calc’d for C C₃₅H₄₃BN₄SSb⁺ [M−BArF₂₄]⁺ 683.2335; found 683.2298
SC-XRD crystal composition note	Crystals measured contained PF₆ as a counterion instead of the expected BArF₂₄ anion
SC-XRD formula	C₄₄H₆₄BF₆N₄PSSb
SC-XRD Dcalc (g cm⁻³)	1.528
SC-XRD μ (mm⁻¹)	0.815
SC-XRD formula weight	958.640
SC-XRD crystal size (mm)	0.20×0.09×0.02
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	triclinic
SC-XRD space group	P−1
SC-XRD a (Å)	12.4126(1)
SC-XRD b (Å)	13.1034(1)
SC-XRD c (Å)	13.4332(1)
SC-XRD α (°)	90.679(1)
SC-XRD β (°)	107.137(1)
SC-XRD γ (°)	93.353(1)
SC-XRD V (Å³)	2083.33(3)
SC-XRD Z	2
SC-XRD Z′	1
SC-XRD wavelength (Å)	0.71073
SC-XRD radiation type	Mo Kα
SC-XRD Θmin (°)	2.19
SC-XRD Θmax (°)	44.98
SC-XRD index range h	−24 ≤ h ≤ 24
SC-XRD index range k	−25 ≤ k ≤ 25
SC-XRD index range l	−24 ≤ l ≤ 26
SC-XRD measured reflections	176707
SC-XRD independent reflections	34138
SC-XRD reflections I≥2σ(I)	27604
SC-XRD Rint	0.0427
SC-XRD parameters	476
SC-XRD restraints	0
SC-XRD largest peak (e Å⁻³)	1.8954
SC-XRD deepest hole (e Å⁻³)	−1.1303
SC-XRD GooF	0.9816
SC-XRD R1 (I≥2σ(I) / all)	0.0338 / 0.0470
SC-XRD wR2 (I≥2σ(I) / all)	0.0787 / 0.0828
SC-XRD CCDC deposition number	258917

Sb(III) complex
Identifier	8
¹H NMR (400 MHz, THF-d₈)	δ: 7.86 (d, ³JH-H = 1.9 Hz, 2 H, H-3), 7.81 – 7.77 (m, 8 H, H-13), 7.58 (bs, 4 H, H-15), 7.09 (d, ³JH-H = 1.9 Hz, 2 H, H-2), 7.07 (d, ³JH-H = 7.8 Hz, 2 H, H-8’), 6.93 (d, ³JH-H = 7.6 Hz, 2 H, H-8), 6.89 (d, ³JH-H = 7.7 Hz, 2 H, H-7’), 6.38 (d, ³JH-H = 7.9 Hz, 2 H, H-7), 2.30 (s, 3 H, H-10’), 2.23 (s, 3 H, H-10), 2.23 (s, 3 H, H-11), 1.87 (s, 18 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, THF-d₈)	δ: 162.5 (q, ¹JC-B = 55.8 Hz, BArF₂₄ C-12), 147.1 (C-5), 146.0 (C-6), 145.5 (C-6’), 138.1 (C-9’), 137.0 (s, C-9), 135.8 (s, BArF₂₄ C-13), 135.5 (s, C-7’), 132.4 (s, C-7), 130.0 (s, C-8’), 129.9 (m, BArF₂₄ C-14), 129.9 (s, C-4), 129.9 (s, C-8), 125.7 (q, ¹JC-F = 273.7 Hz, BArF₂₄ C-16), 122.9 (s, C-3), 118.4 (bs, BArF₂₄ C-15), 62.2 (s, C-2), 32.0 (s, C-1), 21.5 (s, C-10’), 21.4 (s, C-10), 13.4 (s, C-11) ppm
¹⁹F{¹H} NMR (377 MHz, THF-d₈)	δ: −63.38 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, THF-d₈)	δ: 3.15 (bs), −6.53 (bs, BArF₂₄) ppm
HRMS (ASAP-pos, m/z)	calc’d for C₂₉H₃₉BN₄SSb⁺ [M−BArF₂₄]⁺ 607.2022; found 607.2041

Heterotrimetallic Sb(I)-Co complex
Identifier	9
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.56 (d, ³JH-H = 2.0 Hz, 4 H, H-3), 7.07 (d, ³JH-H = 8.0 Hz, 4 H, H-8’), 7.07 (d, ³JH-H = 8.0 Hz, 4 H, H-8), 6.89 (d, ³JH-H = 1.7 Hz, 4 H, H-4), 6.86 (d, ³JH-H = 8.0 Hz, 4 H, H-7’), 6.73 (d, ³JH-H = 8.0 Hz, 4 H, H-7), 2.43 (s, 6 H, H-10’), 2.31 (s, 6 H, H-10), 1.69 (s, 36 H, H-1) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 199.4 (s, C-11 CO), 146.6 (C-6), 140.9 (C-6’) 139.3 (s, C-5), 134.4 (s, C-9), 132.8 (s, C-9’), 132.3 (s, C-7), 130.3 (s, C-7’), 127.7 (s, C-4), 126.2 (s, C-8), 126.0 (s, C-8’), 119.4 (s, C-3), 58.3 (s, C-2), 28.5 (s, C-1), 18.9 (s, C-10’), 18.4 (s, C-10) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: 2.54 (bs) ppm
⁵⁹Co NMR (95 MHz, MeCN-d₃)	δ: −3027.83 (bs, [Co(CO)₄]) ppm
FT-IR (ATR) ν (cm⁻¹)	2111 (bs, CO), 1892 (s, [Co(CO)₄])
HRMS (ASAP-pos, m/z)	calc’d for C₅₉H₇₂B₂CoN₈O₃Sb₂ [M−Co(CO)₄]²⁺ 632.6658; found 632.6660
SC-XRD Sb–Co bond lengths	2.5560(1) Å and 2.5482(1) Å
SC-XRD formula	C₆₅H₇₅B₂Co₂N₉O₇Sb₂
SC-XRD Dcalc (g cm⁻³)	1.435
SC-XRD μ (mm⁻¹)	1.313
SC-XRD formula weight	1477.411
SC-XRD crystal size (mm)	0.20×0.18×0.15
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	triclinic
SC-XRD space group	P−1
SC-XRD a (Å)	14.53379(5)
SC-XRD b (Å)	15.21907(5)
SC-XRD c (Å)	17.73856(6)
SC-XRD α (°)	103.4183(3)
SC-XRD β (°)	110.9362(3)
SC-XRD γ (°)	99.9812(3)
SC-XRD V (Å³)	3419.80(2)
SC-XRD Z	2
SC-XRD Z′	1
SC-XRD wavelength (Å)	0.71073
SC-XRD radiation type	Mo Kα
SC-XRD Θmin (°)	1.56
SC-XRD Θmax (°)	45.30
SC-XRD index range h	−29 ≤ h ≤ 29
SC-XRD index range k	−30 ≤ k ≤ 26
SC-XRD index range l	−35 ≤ l ≤ 35
SC-XRD measured reflections	457812
SC-XRD independent reflections	57120
SC-XRD reflections I≥2σ(I)	52364
SC-XRD Rint	0.0316
SC-XRD parameters	801
SC-XRD restraints	0
SC-XRD largest peak (e Å⁻³)	1.8540
SC-XRD deepest hole (e Å⁻³)	−1.1935
SC-XRD GooF	1.0291
SC-XRD R1 (I≥2σ(I) / all)	0.0205 / 0.0241
SC-XRD wR2 (I≥2σ(I) / all)	0.0467 / 0.0482
SC-XRD CCDC deposition number	258918

Sb(I)-Co complex
Identifier	9′
NMR sample note	Resonances corresponding to the BArF₂₄ anion originating from Sb(II) complex 3-BArF₂₄ were also observed
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.34 (bs, 4 H, H-3), 7.26 (d, ³JH-H = Hz, 4 H, -CH Tol), 7.19 (d, ³JH-H = Hz, 4 H, -CH Tol), 7.03 (bs, 4 H, H-4), 6.45 (d, ³JH-H = Hz, 4 H, -CH Tol), 5.23 (d, ³JH-H = Hz, 4 H, -CH Tol), 2.38 (s, 6 H, -CH₃ Tol), 2.11 (s, 6 H, -CH₃ Tol), 1.69 (s, 36 H, H-1) ppm
¹H NMR assignment note	Unambiguous assignment of the aromatic proton resonances of the tolyl moieties was not possible due to the poor quality of the COSY spectrum
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 197.5 (s, C-11 CO), 145.7 (s), 138.9 (s), 135.8 (s, -C Tol), 129.9 (s, -CH Tol), 127.4 (s, C-4), 120.8 (s, C-3), 103.2 (s, -CH Tol), 101.6 (s, -CH Tol), 30.8 (s, C-1), 21.3 (s, -CH₃ Tol), 20.8 (s, -CH₃ Tol) ppm
¹³C NMR assignment note	Unambiguous assignment of the aromatic carbon resonances of the tolyl moieties was not possible due to the poor quality of the HMBC spectrum
¹¹B NMR (128 MHz, MeCN-d₃)	δ: −0.09 (bs) ppm
⁵⁹Co NMR (95 MHz, MeCN-d₃)	δ: −3027.91 (bs, [Co(CO)₄]) ppm

Sb(III) complex
Identifier	10
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.73 – 7.68 (m, 8 H, H-16), 7.67 (bs, 4 H, H-18), 7.57 (d, ³JH-H = 1.9 Hz, 2 H, H-3), 7.06 (d, ³JH-H = 7.7 Hz, 4 H, H-8), 6.98 (d, ³JH-H = 7.8 Hz, 4 H, H-8’), 6.96 (d, ³JH-H = 1.9 Hz, 4 H, H-4), 6.92 (d, ³JH-H = 7.7 Hz, 4 H, H-7), 6.76 (d, ³JH-H = 7.8 Hz, 4 H, H-7’), 2.29 (s, 3 H, H-10), 2.22 (s, 3 H, H-10’), 1.90 (s, 18 H, H-1) 1.29 (bs, 5 H, H-13 + H-14), 1.16 (bs, 1 H, H-14), 0.58 (s, 12 H, H-12) ppm
¹H–¹H NOESY NMR	NMR cross-peaks between H-12 (TEMPO moiety) and H-8’ and H-7’ (Tolyl moiety in the ligand) were observed
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 162.5 (q, ¹JC-B = 49.8 Hz, BArF₂₄ C-15),155.2 (s, C-5), 147.9 (C-6), 144.7 (C-6’), 137.4 (s, C-9), 136.5 (s, C-9’), 135.6 (s, BArF₂₄ C-16), 135.6 (s, C-7), 132.9 (s, C-7’), 129.8 (m, BArF₂₄ C-17), 129.3 (s, C-8), 129.2 (s, C-4), 129.0 (s, C-8’), 125.3 (q, ¹JC-F = 271.0 Hz, BArF₂₄ C-19), 122.4 (s, C-3), 118.3 (bs, BArF₂₄ C-18), 62.1 (s, C-2), 61.3 (s, C-11), 41.1 (s, C-13 + C-14), 33.8 (s, C-12), 32.7 (s, C-1), 21.2 (s, C-10), 21.1 (s, C-10’), 18.8 (s, C-12) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −63.23 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: −1.20 (bs), −6.68 (bs, BArF₂₄) ppm
HRMS (ASAP-pos, m/z)	calc’d for C₃₇H₅₄BN₅OSb⁺ [M−BArF₂₄]⁺ 716.3455; found 716.3456
SC-XRD formula	C₃₈H₅₄BF₃N₅O₄SSb
SC-XRD Dcalc (g cm⁻³)	1.407
SC-XRD μ (mm⁻¹)	0.782
SC-XRD formula weight	866.529
SC-XRD crystal size (mm)	0.09×0.08×0.02
SC-XRD temperature (K)	100(2)
SC-XRD crystal system	monoclinic
SC-XRD space group	P2₁/c
SC-XRD a (Å)	13.7623(3)
SC-XRD b (Å)	14.9191(2)
SC-XRD c (Å)	20.6134(3)
SC-XRD α (°)	90
SC-XRD β (°)	104.841(2)
SC-XRD γ (°)	90
SC-XRD V (Å³)	4091.18(13)
SC-XRD Z	4
SC-XRD Z′	1
SC-XRD wavelength (Å)	0.71073
SC-XRD radiation type	Mo Kα
SC-XRD Θmin (°)	1.53
SC-XRD Θmax (°)	40.25
SC-XRD index range h	−25 ≤ h ≤ 25
SC-XRD index range k	−26 ≤ k ≤ 27
SC-XRD index range l	−37 ≤ l ≤ 37
SC-XRD measured reflections	236703
SC-XRD independent reflections	25725
SC-XRD reflections I≥2σ(I)	17429
SC-XRD Rint	0.0688
SC-XRD parameters	707
SC-XRD restraints	470
SC-XRD largest peak (e Å⁻³)	1.0268
SC-XRD deepest hole (e Å⁻³)	−0.6433
SC-XRD GooF	1.0028
SC-XRD R1 (I≥2σ(I) / all)	0.0322 / 0.0640
SC-XRD wR2 (I≥2σ(I) / all)	0.0610 / 0.0711
SC-XRD CCDC deposition number	258919

Sb(III) complex
Identifier	11
¹H NMR sample note	Partial decomposition was observed by ¹H NMR. Small amounts of protonated free ligand and 4-bromo-1-butene were detected together with the desired Sb(III) complex 11
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.73 – 7.68 (m, 8 H, H-16), 7.67 (bs, 4 H, H-18), 7.57 (d, ³JH-H = 1.9 Hz, 2 H, H-3), 7.12 (d, ³JH-H = 7.6 Hz, 2 H, H-8), 7.00 (d, ³JH-H = 7.6 Hz, 2 H, H-8’), 6.94 (d, ³JH-H = 7.9 Hz, 2 H, H-7), 6.90 (d, ³JH-H = 1.9 Hz, 2 H, H-4), 6.51 (d, ³JH-H = 7.9 Hz, 2 H, H-7’), 5.39 – 5.29 (m, 1 H, H-13), 4.83 (dm, ³JH-H = 10.2 Hz, 1 H, H-14), 4.72 (dm, ³JH-H = 17.2 Hz, 1 H, H-14), 2.31 (s, 3 H, H-10), 2.24 (s, 3 H, H-10’), 1.98 – 1.91 (m, 2 H, H-12), 1.75 (s, 18 H, H-1), 1.27 – 1.23 (m, 2 H, H-11) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 162.5 (q, ¹JC-B = 49.8 Hz, BArF₂₄ C-15), 147.5 (C-6’), 145.4 (C-6), 143.0 (s, C-5), 139.8 (s, C-13), 138.0 (s, C-9), 137.0 (s, C-9’), 135.6 (s, BArF₂₄ C-16), 135.9 (s, C-7), 131.7 (s, C-7’), 129.9 (m, BArF₂₄ C-17), 129.6 (s, C-8’), 129.5 (s, C-4), 129.4 (s, C-8), 125.3 (q, ¹JC-F = 271.0 Hz, BArF₂₄ C-19), 122.3 (s, C-3), 115.3 (s, C-14), 118.7 (bs, BArF₂₄ C-17), 61.2 (s, C-2), 32.0 (s, C-1), 31.4 (s, C-11), 21.3 (s, C-10’), 21.1 (s, C-10), 20.9 (s, C-12) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −63.23 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: 2.41 (bs), −6.31 (bs, BArF₂₄) ppm
HRMS (ASAP-pos, m/z)	calc’d for C₃₂H₄₃BN₄Sb⁺ [M−BArF₂₄]⁺ 615.2614; found 615.2666

Sb(III) complex
Identifier	12
¹H NMR (400 MHz, MeCN-d₃)	δ: 7.73 – 7.68 (m, 8 H, H-15), 7.67 (bs, 4 H, H-17), 7.58 (d, ³JH-H = 1.9 Hz, 2 H, H-3), 7.12 (d, ³JH-H = 7.5 Hz, 2 H, H-8), 6.99 (d, ³JH-H = 7.5 Hz, 2 H, H-8’), 6.95 (d, ³JH-H = 7.9 Hz, 2 H, H-7), 6.88 (d, ³JH-H = 1.9 Hz, 2 H, H-4), 6.49 (d, ³JH-H = 7.9 Hz, 2 H, H-7’), 2.31 (s, 3 H, H-10), 2.25 (s, 3 H, H-10’), 1.77 (s, 18 H, H-1), 1.18 (d, ³JH-H = 7.6 Hz, 2 H, H-11), 0.67 – 0.56 (m, 1 H, H-12), 0.34 – 0.27 (m, 2 H, H-13), −0.41 – −0.45 (m, 2 H, H-13) ppm
¹³C{¹H} NMR (101 MHz, MeCN-d₃)	δ: 162.5 (q, ¹JC-B = 49.8 Hz, BArF₂₄ C-14), 147.3 (C-6’), 145.4 (C-6), 143.4 (s, C-5), 137.9 (s, C-9), 136.9 (s, C-9’), 135.6 (s, BArF₂₄ C-15), 135.9 (s, C-7), 131.9 (s, C-7’), 129.8 (m, BArF₂₄ C-16), 129.5 (s, C-8’), 129.4 (s, C-4), 129.3 (s, C-8), 125.3 (q, ¹JC-F = 271.0 Hz, BArF₂₄ C-18), 122.4 (s, C-3), 118.3 (bs, BArF₂₄ C-17), 61.3 (s, C-2), 32.0 (s, C-1), 28.5 (s, C-11), 21.3 (s, C-10), 21.1 (s, C-10), 9.5 (s, C-12), 9.0 (s, C-13) ppm
¹⁹F{¹H} NMR (377 MHz, MeCN-d₃)	δ: −63.24 (s, 24 F, BArF₂₄) ppm
¹¹B NMR (128 MHz, MeCN-d₃)	δ: 2.77 (bs), −6.67 (bs, BArF₂₄) ppm
HRMS (ASAP-pos, m/z)	calc’d for C₃₂H₄₃BN₄Sb⁺ [M−BArF₂₄]⁺ 615.2614; found 615.2625

Diethyl 2-(2-bromo-2-phenylethyl)malonate
Identifier	13
¹H NMR (400 MHz, CDCl₃)	δ: 7.40 – 7.28 (m, 5 H), 5.01 (dd, J = 9.1, 6.2 Hz, 1 H), 4.20 (q, J = 7.1 Hz, 6 H), 3.57 (dd, J = 8.4, 6.2 Hz, 1 H), .2.83 – 2.65 (m, 1 H), 2.72 – 2.63 (m, 1 H), 1.27 – 1.24 (m, 4 H), ppm
¹³C{¹H} NMR (101 MHz, CDCl₃)	δ: 168.7, 168.6, 141.0, 129.0, 128.8, 128.7, 127.4, 52.2, 50.8, 38.7, 14.2 ppm

(4-n-perfluorohexyl-2-iodobutoxy)benzene
Identifier	14
¹H NMR (400 MHz, CDCl₃)	δ: 7.32 (t, J = 7.4 Hz, 2 H), 7.02 (t, J = 7.4 Hz, 1 H), 6.93 (d, J = 7.7 Hz, 2 H), 4.56 – 4.50 (m, 1 H), 4.32 – 4.29 (m, 1 H), 4.21 – 4.17 (m, 1 H), 3.27 – 3.13 (m, 1 H), 2.88 – 2.73 (m, 1 H) ppm
¹³C{¹H} NMR (101 MHz, CDCl₃)	δ: 151.6, 129.7, 121.9, 114.9, 72.7, 37.7 (t, J = 21.1 Hz), 12.8 ppm
¹⁹F{¹H} NMR (377 MHz, CDCl₃)	δ: −80.76 – −80.87 (m, 3 F), −113.46 – −113.71 (m, 2 F), −121.75 – −121.84 (m, 2 F), −122.77 – −122.98 (m, 2 F), −123.53 – −123.66 (m, 2 F), −126.14 – −126.20 (m, 2 F) ppm

(1,3,3,3-tetrabromopropyl)benzene
Identifier	15
¹H NMR (400 MHz, CDCl₃)	δ: 7.51 – 7.48 (m, 2 H), 7.41 – 7.30 (m, 3 H), 5.33 (dd, J = 4.1, 7.7 Hz, 1 H), 4.15 – 4.03 (m, 2 H) ppm
¹³C{¹H} NMR (101 MHz, CDCl₃)	δ: 140.9, 129.2, 129.1, 129.0, 128.3, 66.6, 50.2, 35.2 ppm

1-(4-bromobutyl)-1H-indole
Identifier	S6
¹H NMR (400 MHz, CDCl₃)	δ: 7.68 (d, J = 7.9 Hz, 1 H), 7.38 (d, J = 8.2 Hz, 1 H), 7.26 (t, J = 7.6 Hz, 1 H), 7.16 (t, J = 7.4 Hz, 1 H), 7.11 (d, J = 3.1 Hz, 1 H), 6.55 (d, J = 3.1 Hz, 1 H), 4.18 (t, J = 6.9 Hz, 2 H), 3.39 (t, J = 6.5 Hz, 2 H), 2.07 – 1.99 (m, 2 H), 1.90 – 1.83 (m, 2 H) ppm

1-(4-iodobutyl)-1H-indole
Identifier	S7
¹H NMR (400 MHz, CDCl₃)	δ: 7.64 (d, J = 8.5 Hz, 1 H), 7.35 (d, J = 8.2 Hz, 1 H), 7.22 (t, J = 7.3 Hz, 1 H), 7.13 – 7.08 (m, 2 H), 6.51 (d, J = 2.2 Hz, 1 H), 4.16 (t, J = 6.8 Hz, 2 H), 3.16 (t, J = 6.8 Hz, 2 H), 2.02 – 1.94 (m, 2 H), 1.86 – 1.78 (m, 2 H) ppm

6,7,8,9-tetrahydropyrido[1,2-a]indole
Identifier	16
¹H NMR (400 MHz, CDCl₃)	δ: 7.53 (d, J = 7.3 Hz, 1 H), 7.27 (d, J = 7.6 Hz, 1 H), 7.15 – 7.06 (m, 2 H), 6.20 – 6.19 (m, 1 H), 4.05 (t, J = 6.2 Hz, 2 H), 2.98 (t, J = 6.4 Hz, 2 H), 2.12 – 2.06 (m, 2 H), 1.92 – 1.86 (m, 2 H) ppm
¹³C{¹H} NMR (101 MHz, CDCl₃)	δ: 137.3, 136.4, 128.3, 119.7, 119.6, 108.7, 97.6, 42.5, 24.4, 23.6, 21.4 ppm