All reported yields were isolated yields. Flash column chromatography was performed using silica gel (70−230 mesh). 1H NMR spectra were recorded in a 300 MHz NMR spectrometer, using the CDCl3 solvent peak as an internal standard. 13C NMR spectra were recorded at 75.4 MHz. The following abbreviations are used: singlet (s), doublet (d), triplet (t), quartet (q), and multiplet (m). High resolution mass spectra were measured at FAB mode or Electron Impact by JMS-700 HRMS. Melting points were measured with a Yanaco MP500D apparatus and were uncorrected. UV-vis spectra were measured with an HP-8453 spectrophotometer and solvents were of HPLC grades. Fluorescence spectra were measured with an AMINCO−Bowman Series 2 or FluoroMax−3 luminescence spectrometer and solvents were of HPLC grades.
General procedures for the synthesis of 3a, 3b, 3, and 10
To an ice cold solution of o-anisidine 0.18 g (1.50 mmol) in 4 N HCl (4 mL) and acetone (5 mL) was added a solution of NaNO2 (0.20 g, 3.00 mmol) in H2O (5 mL), and the mixture was stirred for 3 h in ice-water bath. The combined solution was added, respectively to another ice cold solution of 2, 7, or 9 (0.60 mmol) in pyridine (10 mL) to produce a colored solution. The reaction mixture was stirred for 1−3 days at 0 oC and then treated with 4 N HCl (50 mL) to give a colored precipitate. The solid residue was purified by column chromatography with ethyl acetate/hexane as an eluent and gave the corresponding products in 20−83% yield.
85
5,17-bis(o-Methoxyphenyl)azo-25,27-dipropargyloxy-26,28-dihydroxycalix−
[4]arene (3a). The solid was eluted with ethyl acetate/hexane (v/v, 1:1) and gave 0.17 g (36%) of an orange powder; mp 213−214 oC; Rf = 0.65 (EtOAc/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 7.77 (4H, s, Ph−H), 7.63 (2H, s, OH), 7.60 (2H, dd, J = 8.0, 1.6 Hz, Ph−H), 7.43−7.37 (2H, m, Ph−H), 7.09−6.94 (8H, m, Ph−H), 6.76 (2H, t, J = 7.5 Hz, Ph−H), 4.83 (4H, d, J = 2.4 Hz, OCH2), 4.44 (4H, d, J = 13.2 Hz, Ph−CH2−Ph), 4.03 (6H, s, OCH3), 3.58 (4H, d, J = 13.2 Hz, Ph−CH2−Ph), 2.63 (2H, t, J = 2.4 Hz, OCH2CCH); 13C NMR (CDCl3, 75.4 MHz) δ 156.7 (Cq), 156.6 (Cq), 151.2 (Cq), 146.7 (Cq), 143.1 (Cq), 133.0 (Cq), 131.8 (CH), 129.6 (Cq), 129.6 (CH), 128.9 (Cq), 126.3 (CH), 124.4 (CH), 121.3 (CH), 117.6 (CH), 112.8 (CH), 78.4 (Cq), 77.6 (CH), 64.0 (CH2), 56.7 (CH3), 32.1 (CH2); MS (FAB, m/z) 769 [M + H+]; HRMS m/z calcd for C48H41N4O6 769.3026, found 769.3028.
5-(o-Methoxyphenyl)azo-25,27-dipropargyloxy-26,28-dihydroxycalix[4]−
arene (3b). The solid was eluted with ethyl acetate/hexane (v/v, 1:2) and gave 0.16 g (42%) of an orange powder; mp 207−209 oC; Rf = 0.73 (EtOAc/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 7.76 (2H, s, Ph−H), 7.63 (1H, s, OH), 7.62−7.58 (1H, m, OH), 7.42−7.37 (1H, m, Ph−H), 7.11−6.99 (5H, m, Ph−H), 6.93 (2H, dd, J = 7.5, 1.5 Hz, Ph−H), 6.86 (2H, dd, J = 7.7, 1.3 Hz, Ph−H), 6.76−6.69 (3H, m, Ph−H), 4.81 (4H, d, J = 2.4 Hz, OCH2), 4.44 (2H, d, J = 13.2 Hz, Ph−CH2−Ph), 4.41 (2H, d, J = 13.2 Hz, Ph−CH2−Ph), 4.03 (3H, s, OCH3), 3.56 (2H, d, J = 13.2 Hz, Ph−CH2−Ph), 3.43 (2H, d, J = 13.2 Hz, Ph−CH2−Ph), 2.60 (2H, t, J = 2.4 Hz, OCH2CCH); 13C NMR (CDCl3, 75.4 MHz) δ 156.8(Cq), 156.6 (Cq), 153.4 (Cq), 151.7 (Cq), 146.6 (Cq), 143.1 (Cq), 133.7 (Cq), 133.1 (Cq), 131.7 (CH), 129.7 (CH), 129.6 (Cq), 129.0 (CH), 128.9 (CH), 128.7 (Cq),
86
126.2 (CH), 124.4 (CH), 121.3 (CH), 119.6 (CH), 117.6 (CH), 112.8 (CH), 78.6 (Cq), 77.6 (CH), 63.9 (CH2), 56.7 (CH3), 32.2 (CH2), 32.1 (CH2); MS (FAB, m/z) 635 [M + H+]; HRMS m/z calcd for C41H35N2O5 635.2546, found 635.2532.
5,17-bis(o-Methoxyphenyl)azo-25,27-bis(1-benzyl-1H-1,2,3-triazolyl−
methyloxy)-26,28-dihydroxycalix[4]arene (4). To a mixture of 3a 0.20 g (0.26 mmol) and 1-(azidomethyl)benzene 0.12 g (0.92 mmol) in THF/H2O 30 mL (v/v, 6:1) was added CuI 2.50 mg (0.01 mmol) and then reflux for 18 h.
After evaporation of solvent, the residue was dissolved in CH2Cl2 and washed thrice with H2O. The organic layer was dried over MgSO4 and the filtrate was concentrated under reduce pressure. The crude product was purified by column chromatography with ethyl acetate/hexane (v/v, 3:1) to afford pure compound 4 0.19 g (71%); mp 256−257 oC; Rf = 0.18 (EtOAc/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 8.08 (2H, s, OH), 7.78 (2H, s, CCHN), 7.70 (4H, s, Ph−H), 7.60 (2H, dd, J = 8.0, 1.62 Hz, Ph−H), 7.43−7.25 (12H, m, Ph−H), 7.09−6.99 (4H, m, Ph−H), 6.94 (4H, d, J = 7.6 Hz, Ph−H), 6.75 (2H, t, J = 7.6 Hz, Ph−H), 5.62 (4H, s, NCH2Ph), 5.21 (4H, s, OCH2), 4.17 (4H, d, J = 13.2 Hz, PhCH2Ph), 4.14 (6H, s, OCH3), 3.37 (4H, d, J = 13.2 Hz, PhCH2Ph); 13C NMR (CDCl3, 75.4 MHz) δ 156.8 (Cq),156.6 (Cq), 151.7 (Cq), 133.0 (Cq),131.8 (CH), 130.0 (Cq), 129.5 (CH), 129.3 (CH), 128.6 (Cq), 128.5 (CH), 126.3 (CH), 124.4 (CH), 124.0 (CH), 121.3 (CH), 117.6 (CH), 112.8 (CH), 70.0 (CH2), 56.7 (CH3), 54.8 (CH2), 31.8 (CH2); MS (FAB, m/z) 1036 [M + H+]; HRMS m/z calcd for C62H54N10O6 1034.4228, found 1034.4235.
87
5-(o-Methoxyphenyl)azo-25,27-bis(1-benzyl-1H-1,2,3-triazolylmethyloxy)- 26,28-dihydroxycalix[4]arene (5). To a mixture of 3b 0.20 g (0.32 mmol) and 1-(azidomethyl)benzene 0.15 g (1.10 mmol) in THF/H2O 30 mL (v/v, 6:1) was added CuI 6.00 mg (0.03 mmol) and then reflux for 18 h. After evaporation of solvent, the residue was dissolved in CH2Cl2 and washed thrice with H2O. The organic layer was dried over MgSO4 and the filtrate was concentrated under reduce pressure. The crude product was purified by column chromatography with ethyl acetate/hexane (v/v, 3:1) to afford pure compound 5 0.21 g (73%); mp 146−147 oC; Rf = 0.25 (EtOAc/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 8.16 (1H, s, OH), 7.77 (2H, s, CCHN), 7.68 (2H, s, Ph−H), 7.60 (1H, dd, J = 8.0, 1.7 Hz, Ph−H), 7.55 (1H, s, OH), 7.41−7.26 (10H, m, Ph−H), 7.09−6.98 (4H, m, Ph−H), 6.91 (2H, dd, J = 7.5, 1.4 Hz, Ph−H), 6.84 (2H, dd, J = 7.7, 1.5 Hz, Ph−H), 6.73−6.64 (3H, m, Ph−H), 5.58 (4H, s, NCH2Ph), 5.17 (4H, s, OCH2C), 4.17 (2H, d, J = 13.1 Hz, PhCH2Ph), 4.16 (2H, d, J = 13.2 Hz, PhCH2Ph), 4.03 (3H, s, OCH3), 3.35 (2H, d, J = 13.2 Hz, PhCH2Ph), 3.26 (2H, d, J = 13.1 Hz, PhCH2Ph); 13C NMR (CDCl3, 75.4 MHz) δ 156.8 (Cq), 156.6 (Cq), 153.4 (Cq), 151.8 (Cq), 146.6 (Cq), 144.3 (Cq), 143.1 (Cq), 135.3 (Cq), 133.6 (Cq), 133.0 (Cq), 131.7 (CH), 129.7 (CH),129.6 (CH),129.5 (CH),129.1 (Cq),128.9 (CH),128.7 (CH), 128.4 (CH),128.2 (CH),126.2 (CH),124.3 (CH),123.9 (CH),121.3 (CH), 119.6 (CH), 117.5 (CH), 112.8 (CH), 70.2 (CH2), 56.7 (CH3), 54.6 (CH2), 31.8 (CH2), 31.7 (CH2); MS (FAB, m/z) 901 [M + H+]; HRMS m/z calcd for C55H48N8O5 900.3748, found 900.3737.
5,17-bis(o-Methoxyphenyl)azo-25,27-bis(1-benzyl-1H-1,2,3-triazolyl−
methyloxy)-26,28-dipropyloxycalix[4]arene (6). To a well stirred solution of 4 0.20 g (0.19 mmol) and NaH 0.14 g (5.78 mmol) in dry DMF (20 mL) was
88
added 1-iodopropane 0.66 g (3.86 mmol) and then stirred at 80 oC for 18 h.
After quenching the NaH by adding MeOH in an ice-water bath, the reaction solution was extracted thrice with CH2Cl2 (20 mL). The organic layer was dried over MgSO4 and the filtrate was evaporated to give the crude product. The crude product was purified by column chromatography with acetone/hexane (v/v, 1:1) to afford pure compound 6 0.03 g (14%); mp 82−84 oC; Rf = 0.28 (EtOAc/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 7.57−7.55 (2H, m, Ph−H), 7.51 (4H, s, C=CHN), 7.42−7.36 (10H, m, Ph), 7.30−7.28 (3H, m, Ph−H), 7.07 (3H, d, J = 8.2 Hz, Ph−H), 6.96 (2H, t, J = 15.2 Hz, Ph−H), 6.32 (6H, d, J = 7.6 Hz, Ph−H), 5.52 (4H, s, NCH2Ph), 5.01 (4H, s, OCH2), 4.29 (4H, d, J = 13.2 Hz, PhCH2Ph), 4.01 (6H, s, OCH3), 3.85 (4H, t, J = 7.9 Hz, OCH2CH2CH3), 3.00 (4H, d, J = 13.5 Hz, PhCH2Ph), 1.75−1.67 (4H, m, OCH2CH2CH3), 0.69 (6H, t, J = 7.41 Hz, OCH2CH2CH3); 13C NMR (CDCl3, 75.4 MHz) δ 161.0 (Cq), 156.9 (Cq), 154.3 (Cq), 148.6 (Cq), 144.9 (Cq), 143.0(Cq), 137.2 (Cq), 135.1 (Cq), 133.8 (Cq), 132.0 (CH), 129.7 (CH), 129.6 (CH), 129.5 (CH), 129.4 (CH), 128.5 (CH), 128.4 (CH), 124.0 (CH), 123.4 (CH), 123.3 (CH), 121.3 (CH), 117.4 (CH), 113.0(CH), 77.2 (CH2), 67.7 (CH2), 56.8 (CH3), 54.6 (CH2), 31.5 (CH2), 23.4 (CH2), 10.4 (CH3); MS (FAB, m/z) 1121 [M + H+]; HRMS m/z calcd for C68H66N10O6 1118.5167, found 1118.5168.
5,17-bis(o-Methoxyphenyl)azo-25,27-dipropyloxy-26,28-dihydroxycalix[4]−
arene (8). The solid was eluted with ethyl acetate/hexane (v/v, 1:3) and gave 0.09 g (39%) of an orange powder; mp 332−334 oC; Rf = 0.9 (EtOAc/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 8.84 (2H, s, OH), 7.75 (4H, s, Ph−H), 7.59 (2H, dd, J = 8.0, 1.68 Hz, Ph−H), 7.41−7.36 (2H, m, Ph−H), 7.08−6.98 (8H, m, Ph−H), 6.78 (2H, t, J = 7.5 Hz, Ph−H), 4.34 (4H, d, J = 13.1 Hz, PhCH2Ph),
89
4.05−4.01 (10H, m, 2OCH3 and 2OCH2CH2CH3), 3.55 (4H, d, J = 13.1 Hz, PhCH2Ph), 2.13−2.07 (4H, m, OCH2CH2CH3), 1.35 (6H, t, J = 7.4 Hz, OCH2CH2CH3); 13C NMR (CDCl3, 75.4 MHz) δ 157.4 (Cq), 156.6 (Cq), 152.2 (Cq), 146.4 (Cq), 143.2 (Cq), 133.1 (Cq), 131.7 (CH), 129.8 (CH), 128.7 (Cq), 125.8 (CH), 124.4 (CH), 121.7 (CH), 117.6 (CH), (CH), 78.8 (CH2), 56.7 (CH3), 31.7 (CH2), 32.9 (CH2), 11.3 (CH3); MS (FAB, m/z) 778 [M + H+]; HRMS m/z calcd for C48H48N4O6 776.3574, found 776.3576.
4-(o-Methoxyphenyl)azo-2,6-dimethylphenol (10). The solid was eluted with ethyl acetate/hexane (v/v, 1:1) and gave 0.52 g (83%) of an orange powder, mp 47−48 oC; Rf = 0.15 (CH2Cl2/hexane, 1:1); 1H NMR (CDCl3, 300 MHz) δ 7.65−7.61 (3H, m, Ph−H), 7.40−7.35 (1H, m, Ph−H), 7.08−6.98 (2H, m, Ph−H), 4.01 (3H, s, OCH3), 2.31 (6H, s, 2CH3); 13C NMR (CDCl3, 75.4 MHz) δ 156.2 (Cq), 146.4 (Cq), 142.0 (Cq), 131.4 (CH), 124.9 (CH), 124.5 (CH), 121.3 (CH), 117.2 (CH), 112.7 (CH), 56.7 (CH3), 16.4 (CH3); MS (EI, m/z) 256 [M+];
HRMS m/z calcd for C15H16N2O2 256.1212, found 256.1207.
5,11,17,23-tetra-t-Butyl-25,26-bis(O-propargyl)calix[4]arene (17) A solution of 5,11,17,23-tetra-t-butylcalix[4]arene (0.5 g, 0.77 mmol), propargyl bromide (0.20 g, 1.70 mmol) in DMF (20 mL) and sodium hydride (0.27 g, 1.92 mmol) was stirred at 70 oC for 2 h. The reaction mixture was extracted twice with CH2Cl2 and the organic solution was dried over MgSO4 and then evaporated to give the sticky crude products. Purification by column chromatography on silica gel eluting with ethyl acetate/hexane (v/v, 2:3) gave pale yellow solid compound 17 (0.31 g, 56%); Rf = 0.9; CH2Cl2/hexane (v/v, 1:1); mp 120−130 oC; 1H NMR (CDCl3, 300 MHz) δ 8.33 (s, 2H, -OH),
90
7.04−7.00 (m, 8H, ph-H), 4.99−4.81 (m, 4H), 4.59 (d, J = 12.8 Hz, 1H), 4.52 (d, J = 13.1 Hz, 2H), 4.37 (d, J = 13.4 Hz, 1H), 3.40 (d, J = 13.2 Hz, 2H), 3.38 (d, J
= 13.5 Hz, 2H), 2.67 (t, J = 2.4 Hz, 2H, alkynyl-H), 1.24 (s, 18H, t-Bu), 1.17 (s, 18H, t-Bu); 13C NMR (CDCl3, 75.4 MHz) δ 151.2 (Cq), 149.3 (Cq), 147.8 (Cq), 143.1 (Cq), 134.3 (Cq), 134.1 (Cq), 129.1 (Cq), 128.9 (Cq), 126.5 (CH), 126.4 (CH), 125.8 (CH), 125.6 (CH), 79.9 (Cq), 76.5 (CH), 62.9 (CH2), 53.7 (CH2), 34.5 (Cq), 34.3 (Cq), 33.1 (CH2), 32.8 (CH2), 32.0 (CH3), 31.7 (CH3); EI-MS m/z 724 (M+); HRMS m/z calcd for C50H60O4 724.4492, found 724.4498.
General procedures for the synthesis of 18, 20, and 22. A solution of 1-azidopyrene (0.25 g, 1.03 mmol) and CuI 1 mg (0.005 mmol) was added to 17 (0.37 g, 0.52 mmol), 19 (0.37 g, 0.52 mmol), and 21 (0.19 g, 1.03 mmol) in THF/H2O (v/v, 2:1, 30 mL), respectively, and the heterogeneous mixture were stirred at 50 oC for 1 d. The mixture was extracted twice with CH2Cl2 and all the organic layers were combined, dried over MgSO4, and then evaporated to give the solid crude products. Column chromatography on silica gel eluting with ethyl acetate and hexane gave white solid compounds 18, 20, and 22 in 74%, 72%, and 79% yield, respectively.
5,11,17,23-tetra-t-Butyl-25,26-bis[(O-methyl)-2H-trizole-1-pyrene]calix[4]−
arene (18) The solid was eluted with ethyl acetate/hexane (v/v, 1:1) and gave 18 (0.45 g, 72%) as a white solid, mp 201−202 oC; Rf = 0.3, ethyl acetate/hexane (v/v, 1:3); 1H NMR (CDCl3, 300 MHz) δ 9.17 (s, 2H), 8.39 (s, 2H), 8.02-7.52 (m, 18H), 7.14 (d, J = 2.4 Hz, 2H), 7.09 (d, J = 2.3 Hz, 2H), 7.04 (d, J = 2.3 Hz, 2H), 7.00 (d, J = 2.3 Hz, 2H), 5.74 (d, J = 11.5 Hz, 2H), 5.16 (d, J = 11.5 Hz, 2H), 4.85 (d, J = 12.7 Hz, 1H), 4.54 (d, J = 12.9 Hz, 2H), 4.29 (d, J = 13.5 Hz, 1H),
91
3.61 (d, J = 12.7 Hz, 1H), 3.45 (d, J =12.9 Hz, 2H), 3.38 (d, J = 13.5 Hz, 1H), 1.23 (s, 18H), 1.19 (s, 18H); 13C NMR (CDCl3, 75.4 MHz) δ 151.8 (Cq), 149.5 (Cq), 147.8 (Cq), 144.6 (Cq), 143.1 (Cq), 134.4 (Cq), 133.6 (Cq), 131.8 (Cq), 131.0 (Cq), 130.4 (Cq), 130.1 (Cq), 129.7 (Cq), 129.4 (Cq), 128.7 (CH), 128.4 (Cq), 127.4 (CH), 126.8 (CH), 126.7 (CH), 126.7 (CH), 126.6 (CH), 126.3 (CH), 126.0 (CH), 126.0 (CH), 125.9 (CH), 125.1 (CH), 124.6 (Cq), 124.5 (CH), 123.8 (Cq), 122.9 (CH), 121.0 (CH), 69.6 (CH2), 34.6 (Cq), 34.3 (Cq), 33.2 (CH2), 31.9 (CH2), 31.9 (CH3), 31.7 (CH3), 30.1 (CH2), 29.7 (CH2); MS (FAB, m/z) 1211 [M+]; HRMS m/z calcd for C82H78N6O4 1210.6085, found 1210.6100.
5,11,17,23-tetra-t-Butyl-25,27-bis[(O-methyl)-2H-trizole-1-pyrene]calix[4]−
arene (20) The solid was eluted with ethyl acetate/hexane (v/v, 1:1) and gave 20 (0.47 g, 74%) as a white solid, mp 196−197 oC; Rf = 0.3, ethyl acetate/hexane (v/v, 1:3); 1H NMR (CDCl3, 300 MHz) δ 8.08 (s, 2H), 8.05−7.62 (m, 18H), 7.30 (s, 2H), 7.11 (s, 4H), 6.87 (s, 4H), 5.32 (s, 4H), 4.40 (d, J = 13.1 Hz, 4H), 3.40 (d, J = 13.1 Hz, 4H), 1.31 (s, 18H), 0.99 (s, 18H); 13C NMR (CDCl3, 75.4 MHz) δ 150.9 (Cq), 150.2 (Cq), 147.9 (Cq), 144.6 (Cq), 142.3 (Cq), 133.0 (Cq), 132.1 (Cq), 131.2 (Cq), 130.7 (Cq), 130.3 (Cq), 129.7 (CH), 128.9 (CH), 127.3 (Cq), 127.1 (CH), 126.9 (CH), 126.5 (CH), 126.4 (CH), 126.2 (CH), 125.8 (CH), 125.7 (CH), 124.9 (CH), 124.1 (Cq), 123.1 (CH), 121.3 (CH), 70.1 (CH2), 34.4 (Cq), 34.3 (Cq), 32.4 (CH2), 32.2 (CH3), 31.5 (CH3); MS (FAB, m/z) 1211 (M+, 0.45), 1234 ([M + Na+], 0.27); HRMS m/z calcd for C82H78N6O4 1210.6085, found 1210.6089.
t-Butylphenyl-(O-methyl)-2H-trizole-1-pyrene (22) The solid was eluted with ethyl acetate/hexane (v/v, 1:1) and gave 7 (0.35 g, 79%) as a white solid,
92
mp 170−171 oC; Rf = 0.6, ethyl acetate/hexane (v/v, 1:3), 1H NMR (CDCl3, 300 MHz) δ 8.32−8.06 (m, 9H), 7.88 (d, J = 9.3 Hz, 1H), 7.38−7.35 (m, 2H), 7.05−7.02 (m, 2H), 5.43 (s, 2H), 1.32 (s, 9H); 13C NMR (CDCl3, 75.4 MHz) δ 156.5 (Cq), 145.1 (Cq), 144.5 (Cq), 132.7 (Cq), 131.5 (Cq), 131.1 (Cq), 130.8 (Cq), 130.2 (CH), 129.4 (CH), 127.4 (CH), 127.2 (CH), 126.9 (CH), 126.8 (CH), 126.6 (Cq), 126.5 (CH), 126.2 (CH), 125.5 (Cq), 125.1 (CH), 124.6 (Cq), 123.8 (CH), 121.5 (CH), 114.7 (CH), 62.7 (CH2), 34.1 (Cq), 31.5 (CH3); MS (EI, m/z) 431 [M+]; HRMS m/z calcd for C29H25N3O 431.1998, found 431.1999.
General procedures for the synthesis of 30−33. A solution of p-substituted- 1-azidobenzene 27−29 (1.03 mmol) and CuI about (1 mg, 0.005 mmol) was added to 19 (0.37 g, 0.52 mmol), and 21 (0.19 g, 1.03 mmol) in THF/H2O (v/v, 2:1, 30 mL), respectively, and the heterogeneous mixture were stirred at 50 oC for 1 day. The mixture was extracted twice with CH2Cl2 and all the organic layers were combined, dried over MgSO4, and then evaporated to give the solid crude products. Column chromatography on silica gel eluting with ethyl acetate and hexane gave white solid compounds 30−33 in 73−85% yield.
5,11,17,23-tetra-t-Butyl-25,27-bis[(O-methyl)-2H-trizole-1-(p-nitrobenzene)]
calix[4]arene (30) The solid was eluted with ethyl acetate/hexane (v/v, 1:3) and gave 30 (0.40 g, 73%) as a yellow solid; mp 199−200 oC; Rf = 0.6, ethyl acetate/hexane (v/v, 1:3); 1H NMR (CDCl3, 300 MHz) δ 8.84 (s, 2H), 8.37 (d, J
= 9.12 Hz, 4H), 7.71 (d, J = 9.12 Hz, 4H), 7.62 (s, 2H), 7.11 (s, 4H), 6.91 (s, 4H), 5.31 (s, 4H), 4.31 (d, J = 13.1 Hz, 4H), 3.41 (d, J = 13.1 Hz, 4H), 1.29 (s, 18H), 1.02 (s, 18H); 13C NMR (CDCl3, 75.4 MHz) δ 150.5 (Cq), 149.6 (Cq), 148.5 (Cq), 147.5 (Cq). 146.8 (Cq), 143.1 (Cq), 140.9 (Cq), 133.0 (Cq), 128.4 (Cq),
93
126.4 (CH), 126.2 (CH), 126.0 (CH), 125.8 (CH), 121.2 (CH), 119.9 (CH), 70.5 (CH2), 34.5 (Cq), 34.3 (Cq), 32.2 (CH2), 32.1 (CH3), 31.4 (CH3); MS (FAB, m/z) 1053 (M+); HRMS m/z calcd for C62H68N8O8 1052.5160, found 1052.5173.
5,11,17,23-tetra-t-Butyl-25,27-bis[(O-methyl)-2H-trizole-1-1benzene]calix[4]
arene (31) The solid was eluted with ethyl acetate/hexane (v/v, 3:5) and gave 31 (0.38 g, 76%) as a white solid; mp 156−157 oC; Rf = 0.5, ethyl acetate/hexane (v/v, 1:3); 1H NMR (CDCl3, 300 MHz) δ 8.66 (s, 2H), 7.51 (s, 3H), 7.39 (s, 8H), 7.09 (s, 3H), 6.86 (s, 3H), 5.32 (s, 4H), 4.32 (d, J = 13.1 Hz, 4H), 3.38 (d, J = 13.1 Hz, 4H), 1.29 (s, 18H), 0.97 (s, 18H); 13C NMR (CDCl3, 75.4 MHz) δ 150.7 (Cq), 149.6 (Cq), 148.2 (Cq), 145.9 (Cq), 142.7 (Cq). 136.8 (Cq), 133.0 (Cq), 130.1 (CH), 129.1 (CH), 128.1 (Cq), 126.2 (CH), 125.7 (CH), 121.0 (CH), 119.8 (CH), 70.8 (CH2), 34.5 (Cq), 34.3 (Cq), 32.1 (CH2), 32.1 (CH3), 31.4 (CH3); MS (FAB, m/z) 963 (M+); HRMS m/z calcd for C62H70N6O4 962.5459, found 963.5450.
5,11,17,23-tetra-t-Butyl-25,27-bis[(O-methyl)-2H-trizole-1-(p-methoxy−
benzene)]calix[4]arene (32) The solid was eluted with ethyl acetate/hexane (v/v, 2:3) and gave 32 (0.43 g, 80%) as a white solid; mp 159−160 oC; Rf = 0.3, ethyl acetate/hexane (v/v, 1:3); 1H NMR (CDCl3, 300 MHz) δ 8.51 (s, 2H), 7.42 (s, 2H), 7.34 (d, J = 9.1, 4H), 7.09 (s, 4H), 6.87 (d, J = 9.1, 4H), 6.85 (s, 4H), 5.30 (s, 4H), 4.31 (d, J = 13.1 Hz, 4H), 3.36 (d, J = 13.1 Hz, 4H), 1.29 (s, 18H), 0.96 (s, 18H); 13C NMR (CDCl3, 75.4 MHz) δ 160.1 (Cq), 150.7 (Cq), 149.7 (Cq), 148.1 (Cq). 145.6 (Cq), 142.6 (Cq), 132.9 (Cq), 130.3 (Cq), 128.1 (Cq), 126.2 (CH), 125.7 (CH), 121.5 (CH), 121.2 (CH), 115.2 (CH), 70.7 (CH2), 56.1 (CH3), 34.4 (Cq), 34.3 (Cq), 32.1 (CH2), 32.1 (CH3), 31.4 (CH3); MS (FAB, m/z) 1023
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(M+); HRMS m/z calcd for C64H74N6O6 1022.5670, found 1022.5670.
t-Butylphenyl-(O-methyl)-2H-trizole-1-(p-nitrobenzene) (33) The solid was eluted with ethyl acetate/hexane (v/v, 3:5) and gave 33 (0.31 g, 85%) as a pale yellow solid; mp 197−198 oC; Rf = 0.5, ethyl acetate/hexane (v/v, 1:3), 1H NMR (CDCl3, 300 MHz) δ 8.43−8.40 (m, 2H), 8.18 (s, 1H), 8.01−7.97 (m, 2H), 7.35−7.32 (m, 2H), 7.00−6.94 (m, 2H), 5.30 (s, 2H), 1.30 (s, 9H); 13C NMR (CDCl3, 75.4 MHz) δ 156.1 (Cq), 147.7 (Cq), 146.7 (Cq), 144.7 (Cq). 141.5 (Cq), 126.9 (CH), 126.0 (CH), 121.1 (CH), 120.9 (CH), 114.5 (CH), 62.3 (CH2), 34.5 (Cq), 31.9 (CH3); MS (EI, m/z) 352 [M+]; HRMS m/z calcd for C19H20N4O3
352.1535, found 352.1534.
General procedures for measurements of the relative quantum yields of ligands 18, and 20 as well as complexes 18⋅Ag+, and 20⋅Ag+. Firstly, the relative quantum yield of pyrene in MeOH/CHCl3 (v/v, 98:2) cosolvent was measured (Table S1) (ΦF of pyrene in EtOH = 0.53 was used)23a based on eqn 2.23
ΦF = (F/Fo) × (Ao/A) × (n/no)2 × ΦFo (eqn 2)
Where A and Ao are the absorbance of the sample and the standard at the excitation wavelength, respectively; F and Fo are the integrated fluorescence emissions of the sample and the standard, respectively; and n and no are solvent refractive indexes of the sample and the standard, respectively.
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Table S1. The data for the quantum yield measurement of pyrene in EtOH or a MeOH/CHCl3 (v/v, 98:2) cosolvent (excitation wavelength = 319 nm).
A (319 nm) F(350-640 nm) F/Fo A/Ao Quantum yield
pyrene1 0.49 50990000 1.00 1.00 0.53
pyrene 0.49 28940000 0.57 0.99 0.29
1. The data of pyrenes was measured in ethanol.
Secondly, the relative fluorescent quantum yields (ΦF) of ligands 18 and 20, and complexes 18⋅Ag+ and 20⋅Ag+ in MeOH/CHCl3 (v/v, 98:2) polar protic cosolvent were determined using pyrene as a standard (ΦF of pyrene in a MeOH/CHCl3 (v/v, 98:2) cosolvent = 0.29 was used) based on eqn 2,23 speratively (Table S2 and S3).
Table S2. The data for the quantum yield measurement of ligand 18 and complex 18⋅Ag+ in a MeOH/CHCl3 (v/v, 98:2) cosolvent using pyrene as the standard (excitation wavelength = 322 nm).
A (322 nm) F(350-640 nm) F/Fo A/Ao Quantum yield
18 0.31 35070000 1.41 1.00 0.40
18⋅Ag+ 0.39 44360000 1.78 0.79 0.40
pyrene 0.31 24950000 1.00 1.00 0.29
Table S3. The data for the quantum yield measurement of ligand 20 and complex 20⋅Ag+ in a MeOH/CHCl3 (v/v, 98:2) cosolvent using pyrene as the standard (excitation wavelength = 320 nm).
A (320 nm) F(350-640 nm) F/Fo A/Ao Quantum yield
20 0.39 54760000 2.11 1.13 0.67
20⋅Ag+ 0.42 65910000 2.54 1.04 0.75
pyrene 0.44 25920000 1.00 1.00 0.28
Finally, all the results are summarized in Table S4.
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Table S4. Relative fluorescent quantum yield (ΦF) of ligands 18 and 20 (10 µM) in the absence and presence of 40 equiv of AgClO4 in a MeOH/CHCl3 (v/v, 98:2) cosolvent, where pyrene was used as a standard (excitation wavelength = 319−322 nm).
pyrene ligand 18 18⋅Ag+ ligand 20 20⋅Ag+
ΦF 0.29 0.40 0.40 0.67 0.75
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