A Divergent Approach to β-Pyrazine-Fused meso-Tetraphenyl­diporphyrins

Abstract

We describe an alternative methodology for the synthesis of β-pyrazine-fused diporphyrins in high yields from 2-amino-5,10,15,20-tetraphenylporphyrin nickel(II) derivatives by using p-dodecylbenzenesulfonic acid as an efficient Brønsted acid catalyst in 1,4-dioxane at 90 °C. The structural characterization, material morphology and electronic properties of the products are reported.

Key words

Brønsted acid catalyst - p-DBSA - β-fused diporphyrins - electrochemistry - HOMO-LUMO energy gap - photophysical properties

• References

• 1a Vicente MG. H. Jaquinod L. Smith KM. Chem. Commun. 1999; 1771
• 1b Anderson HL. Chem. Commun. 1999; 2323
• 1c Arnold DP. Synlett 2000; 296
• 1d Burrell AK. Officer DL. Synlett 1998; 1297
• 1e Holten D. Bocian DF. Lindsay JS. Acc. Chem. Res. 2002; 35: 57
• 1f Kim D. Osuka A. Acc. Chem. Res. 2004; 37: 735
• 1g Hwang IW. Aratani N. Osuka A. Kim D. Bull. Korean Chem. Soc. 2005; 26: 19
• 1h Kim D. Osuka A. J. Phys. Chem. A 2003; 107: 8791
• 1i Tanaka T. Osuka A. Chem. Soc. Rev. 2015; 44: 943
• 1j Sharma R. Gautam P. Shaikh MM. Mishra R. Dalton Trans. 2013; 42: 5539
• 1k Sharma R. Gautam P. Mishra R. Shukla SK. RSC Adv. 2015; 5: 27069
• 2a Crossley MJ. King LG. J. Chem. Soc., Chem. Commun. 1984; 352
• 2b Crossley MJ. Burn PL. J. Chem. Soc., Chem. Commun. 1987; 39
• 2c Crossley MJ. Burn PL. J. Chem. Soc., Chem. Commun. 1991; 1569
• 2d Crossley MJ. Govenlock JL. Prashar JK. J. Chem. Soc., Chem. Commun. 1995; 2379
• 2e Crossley MJ. Johnston LA. Chem. Commun. 2002; 1122
• 2f Khoury T. Crossley MJ. Chem. Commun. 2007; 4851
• 3a Uno H. Hahimoto M. Fujimoto A. Heterocycles 2009; 77: 887
• 3b Uno H. Nakamoto K. Kuroki K. Fujimoto A. Ono N. Chem. Eur. J. 2007; 13: 5773
• 3c Ito S. Nakamoto K. Uno H. Murashima T. Ono N. Chem. Commun. 2001; 2696
• 4 Akita M. Hiroto S. Shinokubo H. Angew. Chem. Int. Ed. 2012; 51: 2894
• 5 Mandoj F. Nardis S. Pudi R. Lvova L. Fronczek FR. Smith KM. Prodi L. Genovese D. Paolesse R. Dyes Pigm. 2013; 99: 136
• 6 Bruhn T. Witterauf F. Gotz DC. G. Grimmer CT. Wurtemberger M. Radius U. Bringmann G. Chem. Eur. J. 2014; 20: 3998
• 7a Nath M. Huffman JC. Zaleski JM. J. Am. Chem. Soc. 2003; 125: 11484
• 7b Nath M. Huffman JC. Zaleski JM. Chem. Commun. 2003; 858
• 7c Nath M. Pink M. Zaleski JM. J. Am. Chem. Soc. 2005; 127: 478
• 7d Boerner LJ. K. Nath M. Pink M. Zaleski JM. Chem. Eur. J. 2011; 17: 9311
• 7e Nath M. Pink M. Zaleski JM. J. Organomet. Chem. 2011; 696: 4152
• 7f Sharma S. Nath M. New J. Chem. 2011; 35: 1630
• 7g Sharma S. Nath M. J. Heterocycl. Chem. 2012; 49: 88
• 7h Sharma S. Nath M. Dyes Pigm. 2012; 92: 1241
• 7i Bhatt RK. Sharma S. Nath M. Monatsh. Chem. 2012; 143: 309
• 7j Sharma S. Nath M. Beilstein J. Org. Chem. 2013; 9: 496
• 7k Singh DK. Nath M. Org. Biomol. Chem. 2015; 13: 1836
• 7l Tiwari R. Nath M. New J. Chem. 2015; 39: 5500
• 7m Tiwari R. Nath M. Dyes Pigm. 2018; 152: 161
• 8 Synthesis of β-pyrazine-fused meso-tetraphenyldiporphyrin nickel(II) analogues 3 and 4To a solution of 2-amino-5,10,15,20-tetraphenylporphyrin nickel(II) (1; 68.5 mg, 0.1 mmol) or 2-amino-12,13-dibromo-5,10,15,20-tetraphenylporphyrin nickel(II) (2; 84.4 mg, 0.1 mmol) in 1,4-dioxane (10 mL), p-dodecylbenzenesulfonic acid (6.52 mg, 0.02 mmol) was added. The reaction mixture was stirred at 90 °C for one hour and the progress of reaction was monitored by TLC. After completion of the reaction, the mixture was diluted with ethyl acetate (40 mL) and washed with water (2 × 40 mL). The organic layer was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated and the crude product was purified by silica gel column chromatography, eluting with 25% chloroform in hexane. The purified product was recrystallized from chloroform/methanol (1:1) solution.
• 9 Analytical data for β-pyrazine-fused meso-tetraphenyldiporphyrin nickel(II) (3): Green solid; yield: 50.5 mg (74%); IR (KBr): 2919, 2850, 1596, 1460, 1442, 1352, 1286, 1178, 1139, 1075, 1008, 909, 831, 797, 750, 717, 699 cm^–1; ¹H NMR (400 MHz, CDCl₃): δ = 8.60 (d, J = 4.9 Hz, 2 H, β-pyrrolic H), 8.59 (d, J = 4.9 Hz, 2 H, β-pyrrolic H), 8.52 (d, J = 4.9 Hz, 2 H, β-pyrrolic H), 8.49 (d, J = 4.9 Hz, 2 H, β-pyrrolic H), 8.02 (d, J = 4.9 Hz, 2 H, β-pyrrolic H), 7.92 (d, J = 4.9 Hz, 2 H, β-pyrrolic H), 8.08–7.91 (m, 10 H, meso-phenyl H), 7.66–7.58 (m, 18 H, meso-phenyl H), 7.41–7.22 (m, 4 H, meso-phenyl H), 7.32–7.30 (m, 4 H, meso-phenyl H), 7.22–7.12 (m, 4 H, meso-phenyl H); UV/Vis (CH₂Cl₂): λ _max (ε × 10^–3) = 422 (186.6), 449 (225.9), 481 (429.3), 577 (80.0), 610 (69.6) nm; MALDI-TOF MS: m/z [M⁺] calcd for C₈₈H₅₂N₁₀Ni₂: 1364.30; found: 1364.30.
• 10 Analytical data for β-pyrazine-fused 12,13,12′,13′-tetrabromo-5,10,15,20-tetraphenyldiporphyrin nickel(II) (4). Grey-green solid; yield: 68.7 mg (82%); IR (KBr): 2924, 1588, 1347, 1055, 1015, 791, 749, 697 cm^–1; ¹H NMR (400 MHz, CDCl₃): δ = 8.59–8.26 (m, 8 H, β -pyrrolic H), 8.08–7.87 (m, 6 H, meso-phenyl H), 7.84–7.79 (m, 4 H, meso-phenyl H), 7.66–7.62 (m, 18 H, meso-phenyl H), 7.47–7.46 (m, 4 H, meso-phenyl H), 7.31–7.29 (m, 4 H, meso-phenyl H), 7.18–7.17 (m, 4 H, meso-phenyl H); UV/Vis (CH₂Cl₂): λ _max (ε × 10^–3) = 432 (366.8), 490 (433.7), 581 (91.5), 629 (96.1) nm; MALDI-TOF MS: m/z [M⁺] calcd for C₈₈H₄₈N₁₀Ni₂Br₄: 1675.95; found: 1675.95.
• 11 Crystallographic data for β-pyrazine-fused meso-tetraphenyldiporphyrin nickel(II) (3) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication data CCDC-1043957
• 12a Ventura B. Flamigni L. Marconi G. Lodato F. Officer DL. New J. Chem. 2008; 32: 166
• 12b Gouterman M. J. Mol. Spectrosc. 1961; 6: 138
• 12c Spellane PJ. Gouterman M. Antipas A. Kim S. Liu YC. Inorg. Chem. 1980; 19: 386
• 13 The electrochemical data were obtained by using a three-electrode CHI 600 D electrochemical analyser, USA. Glassy carbon, platinum wire and Ag/AgCl electrode were used as working, counter and reference electrodes, respectively
• 14a Dolphin D. Niem T. Felton RH. Fujita I. J. Am. Chem. Soc. 1975; 97: 5288
• 14b Johnson EC. Niem T. Dolphin D. Can. J. Chem. 1978; 56: 1381