Molecules 2020, 25, 1607
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120.7, 118.8, 112.4, 56.1. UV-vis (CHCl3): λmax (log
ε
) = 426 (5.53), 513 (3.87), 554 (4.45), 589 (4.04) nm.
HRMS (ESI+): m/z 875.2372. Calcd. for C55H42N7OZn M+· 875.2251.
TZ-POR 6c: δ 9.05 (d, J = 0.8 Hz, 1H, H-3), 8.85–8.82 (m, 4H, β-H),
1H NMR (300 MHz, CDCl3)
8.81 and 8.75 (AB, J = 4.7 Hz, 2H, H-12,13), 8.24–8.17 (m, 8H, H-o-Ph-5,10,15,20), 7.87–7.68 (m, 15H,
H-m,p-Ph-5,10,15,20 + H-o-Ph-o-CH3 + H-p-Ph-o-CH3 + H-5’), 7.39–7.35 (m, 2H, H-m-Ph-o-CH3), 7.32
(d, J = 17.0 Hz, 1H, H-
CDCl3+DMSO d6): 149.9, 149.7, 149.6, 149.5, 149.4, 149.3, 147.8, 147.6,145.7, 145.4, 143.3, 142.8, 142.6,
141.57, 133.9, 131.5 (C-pyrrolic), 131.4 (C-pyrrolic),131.3 (C- pyrrolic), 130.8 (C-3), 129.5, 128.1, 127.0
(C-5’), 126.9 (C- ), 126.7, 126.3, 125.9, 121.7, 121.6, 120.4, 119.9, 119.7, 117.3 (C-m-Ph-o-CH3), 116.9
β), 6.90 (d, J = 17.0 Hz, 1H, H-α
), 1.25 (s, 3H, CH3). 13C RMN (75.5 MHz,
δ
α
(C-m-Ph-o-CH3), 116.5 (C-β), 116.2, 29.0 (CH3). UV-Vis (CHCl3): λmax (log ε) = 428 (5.40), 513 (3.55),
555 (4.24), 589 (4.84) nm. HRMS (ESI+): m/z 859.2432. Calcd. for C55H37N7Zn M+· 859.2402.
TZ-POR 6d: 1H NMR (300 MHz, CDCl3)
δ 9.11 (d, J = 0.5 Hz, 1H, H-3), 8.95–8.91 (m, 4H, β-H),
8.89 and 8.80 (AB, J = 4.7 Hz, 2H, H-12,13), 8.25–8.16 (m, 8H, H-o-Ph-5,10,15,20), 7.83–7.68 (m, 15H,
H-m,p-Ph-5,10,15,20 +H-o-Ph-p-Cl+ H-5’), 7.64–7.56 (m, 2H, H-m-Ph-p-Cl), 7.12 (d, J = 16.3 Hz, 1H,
H-β), 6.84 (d, J = 16.3 Hz, 1H, H-α δ 150.7, 150.69, 150.60, 150.4, 150.3,
). 13C NMR (125.77 MHz, CDCl3)
150.2, 148.6, 148.3, 146.4, 143.4, 142.67, 142.66, 142.3, 135.5, 135.4, 134.6, 134.5, 134.45, 134.42, 134.40,
132.4, 132.3 (H-o-Ph-5,10,15,20), 132.29, 132.27, 132.18, 132.11, 131.6 (C-pyrrolic),131.6 (C-pyrrolic), 130.9
(C-pyrrolic), 130.4, 130.3, 130.2, 130.1, 128.8 (C-3), 128.5 (C-
α
), 127.7, 127.6, 127.6, 127.5, 127.1, 126.9,
), 117.33. UV-Vis (CHCl3)
126.69, 126.62, 126.5, 122.0, 121.5, 121.3, 121.1, 120.9, 120.7, 118.0, 117.37 (C-
β
:
λ
max (log ε
) = 428 (4.97), 554 (3.92), 590 (3.61), 619 (3.39) nm. HRMS (ESI+): m/z 879.1889. Calcd. for
C54H34ClN7Zn M+· 879.1856.
1
TZ-POR 6e: H NMR (300 MHz, CDCl3)
δ
9.11 (d, J = 0.6 Hz, 1H, H-3), 8.94 -8.92 (m, 4H,
β-H), 8.89 and
8.79 (AB, J = 4.7 Hz, 2H, H-12,13), 8.21 -8.18 (m, 8H, H-o-Ph-5,10,15,20), 7.90-7.89 (m, 1H, H-o-Ph-2,4-Cl2),
7.83–7.68 (m, 12H, H-m,p-Ph-5,10,15,20), 7.66 (s, 1H, H-5’), 7.60-7.56 (m, 2H, H-m-Ph-2,4-Cl2), 7.08 (d,
J = 16.2 Hz, 1H, H-β), 6.86 (d, J = 16.2 Hz, 1H, H-α δ 150.8, 150.7,
). 13C NMR (125.77 MHz, CDCl3)
150.6, 150.5, 150.4, 150.3, 148.9, 148.4, 147.0, 146.3, 143.5, 142.7, 142.6, 142.6, 142.0, 141.0, 134.5, 134.4,
132.3, 132.29, 132.24, 132.1, 131.7, 130.5, 129.3, 127.7, 127.5, 126.9, 126.7, 126.62, 126.60, 125.6, 121.6,
121.2, 120.9, 120.6, 120.0, 117.3, 116.9. UV-Vis (CHCl3): λmax (log ε) = 428 (4.89), 553 (3.95), 449 (3.54),
618 (3.41) nm. HRMS (ESI+): m/z 916.1718. Calcd. for C54H33Cl2N7Zn M+· 916.1727
1
TZ-POR 6f: H NMR (300 MHz, CDCl3)
δ 9.13 (s, 1H, H-3), 8.95-8.93 (m, 4H, β-H), 8.90 and 8.81 (AB,
J = 4.7 Hz, 2H, H-12,13), 8.48 (d, J = 9.0 Hz, 2H, H-o-Ph-4-NO2), 8.24 -8.18 (m, 8H, H-o-Ph-5,10,15,20),
7.95 (d, J = 9.0 Hz, 2H, H-m-Ph-p-NO2), 7.85–7.67 (m, 13H, H-m,p-Ph-5,10,15,20 + H-5 ), 7.20 (d, J = 16.4
Hz, 1H, H- ), 6.94 (d, J = 16.4 Hz, 1H, H- 150.8, 150.7, 150.6, 150.5,
).13C NMR (125.77 MHz, CDCl3)
´
β
α
δ
150.4, 150.3, 148.9, 148.4, 147.0, 146.3, 143.5, 142.7, 142.64, 142.63, 142.0, 141.0, 134.5, 134.4, 132.3, 132.29,
132.24, 132.1, 131.7, 130.5, 129.3, 127.7, 127.6, 127.5, 126.9, 126.7, 126.62, 126.60, 125.7, 121.6, 121.2, 120.9,
120.6, 120.0, 117.3, 116.9. UV-Vis (CHCl3): λmax (log ε) = 428 (4.98), 552 (3.78), 450 (3.50), 618 (3.22)
nm. HRMS (ESI+): m/z 446.1144. Calcd. for [C53H36N8O2Zn]2+ 446.1121.
3.1.4. General Procedure for the Decomplexation of TZ-POR 6a–f Derivatives
The demetalation of TZ-POR 6a-f derivatives was made by reaction of 20 mg of each compound
(6a: 0.0236 mmol; 6b: 0.0227 mmol; 6c: 0.0232 mmol; 6d: 0.0227 mmol; 6e: 0.0218 mmol and 6f:
0.0224 mmol) with TFA-CH2Cl2 (9:1) (3 mL), and being stirred in the dark at room temperature for
30 min. Chloroform (10 mL) and water (20 mL) were then added and each mixture was neutralized
with aqueous sodium carbonate and extracted with chloroform (50 mL); the organic phase was then
washed with water (50 mL) and dried over Na2SO4. The solvent was evaporated under reduced
pressure to dryness and the residue was crystallized from chloroform/methanol affording, in each case,
the new TZ-POR 7a–f.