Archimedean solids: Transition metal mediated rational self-assembly of supramolecular-truncated tetrahedra -- Leininger et al. 97 (4): 1380 Data Supplement - Supplementary Material and Methods -- Proceedings of the National Academy of Sciences

Supplementary material for Leininger et al., Proc. Natl. Acad. Sci. USA, 10.1073/pnas.030264697

[(dppf)Pd(OTf)₂]₆[1,3,5-tris(4
'-pyridylethynyl)benzene]₄ (5). To a solution of 15.4 mg (0.0161 mmol) of 3 in 3 ml of CH₂Cl₂ was added 4.2 mg (0.011 mmol) of 1 in 2 ml of CH₂Cl₂. After 1 h the solvent was evaporated and the product crystallized from CH₂Cl₂. Yield: 16.8 mg (88%). Mp = 172-180 (dec.). ¹H NMR (CD₂Cl₂, 300 MHz): d 8.70 (br, s, 24 H, py-H_a), 7.87 (m, 48 H, PPh-H_o), 7.61 (m, 72 H, PPh-H_p,m), 7.51 (s, 12 H, Ph-H), 7.02 (d, J = 5.4 Hz, 24 H, py-H_b), 4.80 (s, 24 H, PCp-H_a), 4.62 (s, 24 H, PCp-H_b). ³¹P{¹H} NMR (CD₂Cl₂, 121 MHz): d 34.1 (s). ¹³C{¹H} NMR (CD₂Cl₂, 75 MHz): d 150.9 (s, py-C_a), 137.5 (s, py-C_g), 134.7 (d, J = 11.6 Hz, PPh-C_o), 134.2 (s, PPh-C_p), 133.5 (s, py-C_b), 130.4 (d, J = 11.0 Hz, PPh-C_m), 128.7 (s, (-CC-)₃Ph-C_o), 127.8 (d, J_P-C = 56.1 Hz, PPh-C_i), 123.0 (s, (-CC-)₃Ph-C_i), 121.6 (q, J_F-C = 319 Hz, C_OTf), 95.8 (s, py-CC-), 87.3 (s, py-CC-), 77.5 (m, PCp-C_a), 76.1 (m, PCp-C_b), 68.1 (m, PCp-C_i). ¹⁹F NMR (CD₂Cl₂, 282 MHz): d -77.7 (s). IR (neat, cm^-1): 3345, 3228, 3102, 2367, 2212, 2064, 1603, 1440, 1247, 1146, 1026. UV-VIS [l , nm, in CH₂Cl₂ (e ´ 10⁴, cm^-1∙M^-1)]: 232 (27.8), 308 (42.9), 325 (46.9). Anal. for C₃₂₄H₂₂₈F₃₆Fe₆N₁₂O₃₆P₁₂Pd₆S₁₂·12H₂O, Calcd. C, 51.92; H, 3.39; N, 2.24; S, 5.13. Found: C, 51.74; H, 3.42; N, 2.25; S, 4.89. MS (ES): 3489 [calcd for (M – 2 OTf)²⁺: 3487], 2276 [calcd for (M – 3 OTf)³⁺: 2275], 1670 (calcd for (M – 4 OTf)⁴⁺: 1669]. [(dppf)Pd(OTf)₂]₆[1,3,5-tris(4
'-cyanophenylethynyl)benzene]₄ (6). To a solution of 10.5 mg (0.0109 mmol) of 3 in 3 ml of CH₂Cl₂ was added 3.3 mg (0.0073 mmol) of 2 in 2 ml of CH₂Cl₂. Crystallization from CH₂Cl₂ gave 11.9 mg of a deep red solid. Yield: 87%. Mp = 203-205 (dec.). ¹H NMR (CD₂Cl₂, 300 MHz): d 7.91-7.84 (m, 48 H, PPh-H_o), 7.72 (s, 12 H, (-CC-)₃Ph-H), 7.66 (m, 24 H, PPh-H_p), 7.58 (s, 24 H, NC-Ph-H_o), 7.57 (s, 24 H, NC-Ph-H_m), 7.53 (m, 48 H, PPh-H_m), 4.68 (s, 24 H, PCp-H_a), 4.62 (s, 24 H, PCp-H_b). ³¹P{¹H} NMR (CD₂Cl₂, 121 MHz): d 46.1 (s). ¹³C{¹H} NMR (CD₂Cl₂, 75 MHz): d 135.6 (s, NC-Ph-C_i), 134.7 (t, J = 6.0 Hz, PPh-C_o), 133.7 (s, PPh-C_p), 133.4 (s, NC-Ph-C_o), 132.6 (s, NC-Ph-C_m), 130.0 (t, J = 6.0 Hz, PPh-C_m), 129.0 (m, PPh-C_i), 128.3 (s, NC-Ph-C_p), 124.0 (s, (-CC-)₃Ph-C_o), 120.9 (q, J = 318 Hz, CF₃SO₃), 120.5 (s, (-CC-)₃Ph-C_i), 110.6 (s, NC), 92.3 (s, NC-Ph-CC-), 89.7 (s, NC-Ph-CC-), 78.8 (t, J = 6.0 Hz, PCp-C_a), 76.4 (s, PCp-C_b), 69.9 (d, J_P-C = 75 Hz, PCp-C_i). ¹⁹F NMR (CD₂Cl₂, 282 MHz): d -77.7 (s). IR (neat, cm^-1): 3256, 3054, 2259, 2224, 1597, 1435, 1233, 1094, 1027. UV-VIS [l , nm, in CH₂Cl₂ (e ´ 10⁴, cm^-1∙M^-1)]: 230 (36.2), 300 (62.4), 320 (65.1), 388 (4.2). Anal. for C₃₄₈H₂₂₈F₃₆Fe₆N₁₂O₃₆P₁₂Pd₆S₁₂·6H₂O, Calcd. C, 54.46; H, 3.15; N, 2.19; S, 5.00. Found: C, 54.23; H, 3.34; N, 2.35; S, 5.09. [(dppf)Pt(OTf)₂]₆[1,3,5-tris(4
'-pyridylethynyl)benzene]₄ (7). To a solution of 11.4 mg (0.0109 mmol) of 4 in 3 ml of CH₃NO₂ was added 2.8 mg (0.0073 mmol) of 1. The mixture was heated at 50° C for 20 h, resulting in a clear yellow solution. After crystallization 11.7 mg of a yellow solid was collected. Yield: 82 %. Mp = 187-190 (dec.). ¹H NMR (CD₃NO₂, 300 MHz) d 8.42 (br, d, J = 3.9 Hz, 24 H, py-H_a), 7.97 (m, 48 H, PPh-H_o), 7.73 (m, 24 H, PPh-H_p), 7.68 (s, 12 H, Ph-H), 7.65 (m, 48 H, PPh-H_m), 7.19 (d, J = 6.3 Hz, 24 H, py-H_b), 4.81 (s, 24 H, PCp-H_a), 4.72 (s, 24 H, PCp-H_b). ³¹P{¹H} NMR (CD₃NO₂, 121 MHz): d 6.0 (s, ¹⁹⁵Pt satellite, J_Pt-P = 3388 Hz). ¹³C{¹H} NMR (CD₃NO₂, 75 MHz): d 151.0 (s, py-C_a), 138.7 (s, py-C_g), 136.1 (s, PPh-C_p), 135.5 (m, PPh-C_o), 134.5 (s, py-C_b), 131.1 (m, PPh-C_m), 130.5 (s, (-CC-)₃Ph-C_o), 127.8 (m, PPh-C_i), 123.8 (s, (-CC-)₃Ph-C_i), 122.4 (q, J_F-C = 319 Hz, C_OTf), 97.1 (s, py-CC-), 87.6 (s, py-CC-), 77.5 (m, PCp-C_a,b), 68.1 (m, PCp-C_i). ¹⁹F NMR (CD₃NO₂, 282 MHz): d -77.5 (s). IR (neat, cm^-1): 3391, 3120, 2362, 2343, 2211, 1616, 1436, 1277, 1257, 1154, 1029. UV-VIS [l , nm, in CH₂Cl₂ (e ´ 10⁴, cm^-1M^-1)]: 232 (6.4), 310 (10.1), 328 (11.5). Anal. for C₃₂₄H₂₂₈F₃₆Fe₆N₁₂O₃₆P₁₂Pt₆S₁₂·6H₂O, Calcd. C, 49.14; H, 3.05; N, 2.12; S, 4.80. Found: C, 48.84; H, 2.98; N, 2.21; S, 4.84. MS (ES): 3756 [calcd for (M – 2 OTf)²⁺: 3754], 2454 [calcd for (M – 3 OTf)³⁺: 2453], 1804 [calcd for (M – 4 OTf)⁴⁺: 1803], 1413 [calcd for (M – 5 OTf)⁵⁺: 1412], 1153 [calcd for (M – 6 OTf)⁶⁺: 1152]. [(dppf)Pt(OTf)₂]₆[1,3,5-tris(4
'-cyanophenylethynyl)benzene]₄ (8). To a solution of 11.5 mg (0.0110 mmol) of 4 in 3 ml of CH₂Cl₂ was added 3.3 mg (0.0073 mmol) of 2 in 2 ml of CH₂Cl₂. Recrystallization from CH₂Cl₂ gave diamond-shaped orange crystals. Yield: 75%. Mp = 224-227 (dec.). ¹H NMR (CD₂Cl₂, 300 MHz): d 7.91-7.84 (m, 48 H, PPh-H_o), 7.72 (s, 12 H, (-CC-)₃Ph-H), 7.59 – 7.49 (m, 120 H, PPh-H_p,m, NC-Ph-H_o,m), 4.63 (s, 24 H, PCp-H_a), 4.57 (s, 24 H, PCp-H_b). ³¹P{¹H} NMR (CD₃NO₂, 121 MHz): d 10.2 (br, s). ¹³C{¹H} NMR (CD₂Cl₂, 75 MHz): d 135.6 (s, NC-Ph-C_i), 134.6 (d, J = 12 Hz, PPh-C_o), 133.6 (s), 132.6 (s), 129.9 (d, J = 12 Hz, PPh-C_m), 127.9 (br, m), 123.9 (s), 121.4 (q, J = 320 Hz, CF₃SO₃), 92.4 (br, m), 89.7 (s, NC-Ph-CC-), 77.7 (d, J = 12.5 Hz, PCp-C_a), 76.1 (d, J = 8.6 Hz, PCp-C_b), 68.2 (d, J_P-C = 81 Hz, PCp-C_i). ¹⁹F NMR (CD₂Cl₂, 282 MHz): d -77.7 (s). IR (neat, cm^-1): 3391, 3120, 2864, 2362, 2340, 2272, 1602, 1436, 1260, 1154, 1027. UV-VIS [l , nm, in CH₂Cl₂ (e ´ 10⁴, cm^-1M^-1)]: 232 (30), 300 (46.9), 320 (51.4). Anal. for C₃₄₈H₂₂₈F₃₆Fe₆N₁₂O₃₆P₁₂Pt₆S₁₂∙6H₂O, Calcd. C, 50.91; H, 2.95; N, 2.05; S, 4.68. Found: C, 50.82; H, 2.99; N, 2.23; S, 4.51. [(Et₃P)₂Pd(OTf)₂]₆[1,3,5-tris(4
'-pyridylethynyl)benzene]₄ (11). To a solution of 20.0 mg (0.0313 mmol) of 9 in 3 ml of CH₃NO₂ was added slowly 8.0 mg (0.0208 mmol) of 2. After 1 h Et₂O was added and the product was precipitated. Yield: 24.8 mg (89%). Mp = 168-170 (dec.). ¹H NMR (CD₃NO₂, 300 MHz): d 8.96 (d, J = 5.1 Hz, 24 H, py-H_a), 7.92 (s, 12 H, Ph-H), 7.73 (d, J = 6.0 Hz, 24 H, py-H_b), 1.98 (m, 72 H, PCH₂), 1.38 (m, 108 H, PCH₂CH₃). ³¹P{¹H} NMR (CD₃NO₂, 121 MHz): d 30.9 (s). ¹³C{¹H} NMR (CD₃NO₂, 75 MHz): d 151.4 (s, py-C_a), 138.7 (s, py-C_g), 136.5 (s, py-C_b), 130.8 (s, (-CC-)₃Ph-C_o), 124.0 (s, (-CC-)₃Ph-C_i), 122.5 (q, J_F-C = 319 Hz, C_OTf), 96.9 (s, py-CC-), 88.0 (s, py-CC-), 17.0 (t, J = 15.5 Hz, PCH₂), 8.6 (s, PCH₂CH₃). ¹⁹F NMR (CD₃NO₂, 282 MHz): d -77.6 (s). IR (neat, cm^-1): 3143, 2345, 1612, 1442, 1251, 1153. [(Et₃P)₂Pt(OTf)₂]₆[1,3,5-tris(4
'-pyridylethynyl)benzene]₄ (12). A total of 6.9 mg (0.0182 mmol) of 1 were dissolved in 2 ml of CH₂Cl₂ and slowly added to a solution of 20.9 mg (0.0273 mmol) of 10 in 3 ml of acetone. Recrystallization from acetone/hexanes 1:1 yielded 24.1 mg of a white crystalline solid. Yield: 87%. Mp = 254-259 (dec.). ¹H NMR (CD₃CO, 300 MHz): d 9.32 (d, J = 4.1 Hz, 24 H, py-H_a), 8.02 (s, 12 H, Ph-H), 7.84 (d, J = 4.1 Hz, 24 H, py-H_b), 2.04 (m, 72 H, PCH₂), 1.36 (m, 108 H, PCH₂CH₃). ³¹P{¹H} NMR (CD₃CO, 121 MHz): d 5.3 (s, ¹⁹⁵Pt satellite, J_Pt-P = 3095 Hz). ¹³C{¹H} NMR (CD₃NO₂, 75 MHz): d 151.8 (s, py-C_a), 138.6 (s, py-C_g), 136.6 (s, py-C_b), 131.2 (s, (-CC-)₃Ph-C_o), 124.0 (s, (-CC-)₃Ph-C_i), 122.0 (q, J_F-C = 319 Hz, C_OTf), 97.6 (s, py-CC-), 88.0 (s, py-CC-), 13.2 (t, J = 13.1 Hz, PCH₂), 8.2 (s, PCH₂CH₃). ¹⁹F NMR (CD₃NO₂, 282 MHz): d -79.4 (s). IR (neat, cm^-1): 3150, 2332, 1632, 1444, 1277. Anal. for C₁₉₂H₂₄₀F₃₆N₁₂O₃₆P₁₂Pt₆S₁₂·12H₂O, Calcd. C, 37.65; H, 4.31; N, 2.75; S, 6.28. Found: C, 37.78; H, 4.25; N, 2.76; S, 6.21. MS (ES): 2802 [calcd for (M – 2 OTf)²⁺: 2800], 1817 [calcd for (M – 3 OTf)³⁺: 1818], 1326 [calcd for (M – 4 OTf)⁴⁺: 1326)]. [5,10-Di(4
'-pyridyl)-15,20-diphenylporphyrin]₆[1,3,5-tris[(trans-(PEt₃)₂Pt(OTf)₂)ethynyl]benzene]₄(15). To a solution of 9.8 mg (0.016 mmol) of 13 in 5 ml of CH₂Cl₂ was slowly added a solution of 20.0 mg (0.011 mmol) of 14 in a mixture of CHCl₃ and CH₃OH (3:1, 10 ml). The resulting mixture was stirred for 10 h at room temperature. Recrystallization gave a deep red solid. Yield: 26 mg (87%). Mp = 247 - 250 (dec.). ¹H NMR (CD₂Cl₂/CDCl₃/CD₃OD, 300 MHz): d 9.20 (br, s, 24 H, py-H_a), 8.93 (m, 48 H, por-H), 8.64 (br, s, 24 H, py-H_b), 8.23 (m, 24 H, ph-H_o), 7.78 (m, 36 H, ph-H_p,m), 7.29 (s, 12 H, ben-H), 2.16 (m, 144 H, P-CH₂), 1.44 (m, 216 H, P-CH₂-CH₃). ³¹P{¹H} NMR (CD₂Cl₂, 121 MHz): d 19.8 (s, ¹⁹⁵Pt satellite, J_Pt-P = 2287 Hz). ¹⁹F NMR (CD₂Cl₂, 282 MHz): d -73.3 (s). ¹³C{¹H} NMR (CD₂Cl₂/CDCl₃/CD₃OD, 125 MHz): d 153.3 (s, py-C_g), 149.3 (s, py-C_a), 141.6 (s), 134.9 (s, py-C_b), 128.4, 127.1, 125.7 (m), 124.0, 122.7, 121.3 (q, J = 320 Hz, OTf), 120.5, 114.7, 92.3, 89.7 (m), 13.2 (m, CH₂), 8.2 (s, CH₃). UV-VIS [l , nm, in CH₂Cl₂ (e ´ 10⁴, cm^-1M^-1)]: 250 (21.4), 310 (20.5), 420 (125.7), 518 (9.6), 554 (5.4), 588 (5.0), 648 (4.0). Anal. for C₄₅₆H₅₄₀F₃₆N₃₆O₃₆P₂₄Pt₁₂S₁₂∙6H₂O∙3CHCl₃, Calcd. C, 47.04; H, 4.77; N, 4.30; S, 3.28. Found: C, 46.67; H, 4.76; N, 4.12; S, 3.34.