Compound 2

8-(((N'-(1-heptyloctyl)terrylene-3,4:11,12-tetracarboxydiimide-N-yl)-triptycen-1-yl)-[1,1'-biphenyl]-4-yl)-N'-(1-heptyloctyl)terrylene-3,4:11,12-bis(dicarboximide)

From: Enabling singlet fission by controlling intramolecular charge transfer in π-stacked covalent terrylenediimide dimers

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Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

Synthesis of precursor P5: prepared via same general procedure as synthesis of P3 outlined in synthesis of 0. The product was collected as an off-while solid (62 mg, 63%). 1H NMR (500 MHz, CDCl3) δ 8.76 (dd, J = 7.1, 1.1 Hz, 2H), 8.61 (dd, J = 7.2, 1.3 Hz, 1H), 8.54 (dd, J = 7.2, 1.2 Hz, 1H), 8.35 (dd, J = 8.3, 1.2 Hz, 2H), 8.22 (dd, J = 8.3, 1.2 Hz, 1H), 8.16 (dd, J = 8.2, 1.2 Hz, 1H), 7.88 (dd, J = 8.3, 7.2 Hz, 2H), 7.72 (dd, J = 8.2, 7.2 Hz, 1H), 7.63 (dd, J = 8.3, 7.2 Hz, 1H), 7.52 – 7.49 (m, 1H), 7.48 – 7.41 (m, 2H), 7.32 (d, J = 8.3 Hz, 2H), 7.29 – 7.27 (m, 2H), 7.18 – 7.00 (m, 6H), 6.99 – 6.91 (m, 5H), 5.60 (s, 1H), 5.33 (s, 1H). 13C NMR (126 MHz, CDCl3) δ 164.59, 163.95, 163.62, 147.17, 147.10, 145.74, 145.32, 144.10, 142.82, 141.97, 140.54, 140.07, 139.71, 137.59, 135.15, 134.66, 134.49, 132.13, 131.89, 131.80, 131.75, 131.58, 131.55, 131.31, 130.40, 130.36, 129.36, 129.27, 128.68, 128.35, 127.56, 127.50, 127.16, 126.54, 126.49, 126.40, 126.07, 125.75, 125.62, 125.36, 125.33, 124.89, 124.41, 123.97, 123.61, 123.05, 122.90, 122.57, 122.23, 119.32, 54.45, 46.80. MS (MALDI-TOF): m/z calcd for C56H32N2O4, [M]- 796.23, found 796.22.

Prepared via same general procedure as 0. The product was collected as a blue solid (25 mg, 29 %). Spectroscopic samples were further purified by HPLC (HP Agilent 1100). 1H NMR (500 MHz, C2D2Cl4) δ 8.80 – 8.53 (m, 14H), 8.52 – 8.15 (m, 8H), 7.63 – 6.91 (m, 18H), 6.81 (d, J = 7.6 Hz, 2H) 5.64 (s, 1H), 5.26 (m, 1H), 5.02 (s, 1H), 4.91 (m, 1H), 2.32 (m, 12H), 1.73 (m, 8H), 1.44 (m, 28H), 0.94 (m, 12H). 13C NMR was not obtained due to sparing solubility. MS (MALDI-TOF): m/z calcd for C130H106N4O8, [M]- 1851.80, found 1851.67.