Basic Photophysical Properties of meso-Bis(pyren-2-yl)porphyrin: An Isomer of Pyrene-Substituted Porphyrins

Abstract

The Suzuki–Miyaura coupling reaction of pyren-2-yl boronic acid ester with a meso-dibromodiphenylporphyrin derivative was carried out to give another pyrene-substituted porphyrin. The electrophilic substitution reaction occurred selectively on the porphyrin nucleus of this molecule. The introduced pyrenes acted as a light-harvesting antenna.

Key words

porphyrin - pyrene - Suzuki–Miyaura coupling - light-harvesting­

• References

• 1 Kadish K, Guilard R, Smith KM. The Porphyrin Handbook Vol. 1-20 . Academic Press; Amsterdam: 2003
• 2 Mori H, Tanaka T, Osuka A. J. Mater. Chem. C 2013; 1: 2500
• 3 Mikami S, Sugiura K.-i, Sakata Y. Chem. Lett. 1997; 833
• 4 Wasielewski MR, Johnson DG, Svec WA, Kersey KM, Minsek DW. J. Am. Chem. Soc. 1988; 110: 7219
• 5 Diev VV, Schlenker CW, Hanson K, Zhong Q, Zimmerman JD, Forrest SR, Thompson ME. J. Org. Chem. 2012; 77: 143
• 6 Englert JM, Malig J, Zamolo VA, Hirsch A, Jux N. Chem. Commun. 2013; 49: 4827
• 7 Yamane O, Sugiura K.-i, Miyasaka H, Nakamura K, Fujimoto T, Nakamura K, Kaneda T, Sakata Y, Yamashita M. Chem. Lett. 2004; 33: 40
• 8 Crawford AG, Liu Z, Mkhalid IA. I, Thibault M.-H, Schwarz N, Alcaraz G, Steffen A, Collings JC, Batsanov AS, Howard JA. K, Marder TB. Chem. Eur. J. 2012; 18: 5022
• 9 Blake IM, Anderson HL, Beljonne D, Brédas J.-L, Clegg W. J. Am. Chem. Soc. 1998; 120: 10764

We were unable to obtain good elemental analysis values for pyrene-substituted porphyrins. meso-Tetraphenylporphryin (TPP) and its metal complexes are known to behave as porphyrin sponges in which the TPP lattices incorporate solvent molecules like a sponge, see:
• 10a Byrn MP, Curtis CJ, Khan SI, Sawin PA, Tsurumi R, Strouse CE. J. Am. Chem. Soc. 1990; 112: 1865
• 10b Byrn MP, Strouse CE. J. Am. Chem. Soc. 1991; 113: 2501
• 10c Byrn MP, Curtis CJ, Goldberg I, Hsiou Y, Khan SI, Sawin PA, Tendick SK, Strouse CE. J. Am. Chem. Soc. 1991; 113: 6549
• 10d Byrn MP, Curtis CJ, Hsiou Y, Khan SI, Sawin PA, Tendick SK, Terzis A, Strouse CE. J. Am. Chem. Soc. 1993; 115: 9480 . Because pyrene is larger than benzene, the space of the lattice produced by 3(M) and/or 7 should be larger than that produced by TPP. For example, the crystal of 7 incorporated two toluene molecules in its unit cell.¹² The incorporation of solvent molecules could be one of the reasons for the inaccurate EA values. The characterization of new products was based on high-resolution mass spectroscopic analysis
• 11 Crossley MJ, Burn PL, Chew SS, Cuttance FB, Newsom IA. Chem. Commun. 1991; 1564
• 12 Preliminary single-crystal diffraction study of 7 was carried out (see Figure 2). However, the marked disorder of solvent molecules prevented the complete analysis. Provisional results are shown in the Supporting Information SI2. CCDC 1520375 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 13a Yoshinaga T, Hiratsuka H, Tanizaki Y. Bull. Chem. Soc. Jpn. 1977; 50: 3096
• 13b Yamashita K.-i, Nakamura A, Sugiura K.-i. Chem. Lett. 2015; 44: 303
• 14 Yamashita K.-i, Nakamura A, Hossain MA, Hirabayashi K, Shimizu T, Sugiura K.-i. Bull. Chem. Soc. Jpn. 2015; 88: 1083
• 15 Similar experiments were carried out in polar solvent DMF and similar results were obtained; that is, energy transfer occurred from pyrenes to porphyrin.
• 16 One of the objectives of this study was to synthesize pyrene-fused porphyrins. Attempts to obtain such porphyrins under oxidative conditions, such as FeCl₃ in MeNO₂, DDQ/Sc(OTf)₃, etc., were unsuccessful. Furthermore, Pd-catalyzed intramolecular C–C bond formation reactions on tetrabromide 7 also failed, see: Saegusa Y, Ishizuka T, Komamura K, Shimizu S, Kotani H, Kobayashi N, Kojima T. Phys. Chem. Chem. Phys. 2015; 17: 15001 ; details of the oxidation reactions of 3(M) will be reported elsewhere
• 17 Dien LX, Yamashita K.-i, Asano MS, Sugiura K.-i. Inorg. Chim. Acta 2015; 432: 103
• 18 Hassan K, Yamashita K.-i, Hirabayashi K, Shimizu T, Nakabayashi K, Imai Y, Matsumoto T, Yamano A, Sugiura K.-i. Chem. Lett. 2015; 44: 1607