Near-Infrared-III-Absorbing and -Emitting Dyes: Energy-Gap Engineering of Expanded Porphyrinoids via Metallation
Yue Wang
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
These authors contributed equally to this work.
Search for more papers by this authorKoki Ogasahara
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
These authors contributed equally to this work.
Search for more papers by this authorDaisuke Tomihama
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorDr. Radomir Mysliborski
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorCorresponding Author
Dr. Masatoshi Ishida
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorYongseok Hong
Department of Chemistry and Spectroscopy for Functional π-Electronic Systems, Yonsei University, Seoul, 03722 Korea
Search for more papers by this authorYusuke Notsuka
Graduate School of Advanced Health Sciences, Saga University, Saga, 840-8502 Japan
Search for more papers by this authorProf. Dr. Yoshihisa Yamaoka
Graduate School of Advanced Health Sciences, Saga University, Saga, 840-8502 Japan
Search for more papers by this authorTomotaka Murayama
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo, 113-0033 Japan
Search for more papers by this authorDr. Atsuya Muranaka
Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory, RIKEN, Saitama, 351-0198 Japan
Search for more papers by this authorProf. Dr. Masanobu Uchiyama
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo, 113-0033 Japan
Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory, RIKEN, Saitama, 351-0198 Japan
Search for more papers by this authorDr. Shigeki Mori
Advanced Research Support Center, Ehime University, Matsuyama, 790-8577 Japan
Search for more papers by this authorDr. Yuhsuke Yasutake
Graduate School of Arts and Sciences, The University of Tokyo, Tokyo, 153-8902 Japan
Search for more papers by this authorProf. Dr. Susumu Fukatsu
Graduate School of Arts and Sciences, The University of Tokyo, Tokyo, 153-8902 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Dongho Kim
Department of Chemistry and Spectroscopy for Functional π-Electronic Systems, Yonsei University, Seoul, 03722 Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Hiroyuki Furuta
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorYue Wang
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
These authors contributed equally to this work.
Search for more papers by this authorKoki Ogasahara
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
These authors contributed equally to this work.
Search for more papers by this authorDaisuke Tomihama
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorDr. Radomir Mysliborski
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorCorresponding Author
Dr. Masatoshi Ishida
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorYongseok Hong
Department of Chemistry and Spectroscopy for Functional π-Electronic Systems, Yonsei University, Seoul, 03722 Korea
Search for more papers by this authorYusuke Notsuka
Graduate School of Advanced Health Sciences, Saga University, Saga, 840-8502 Japan
Search for more papers by this authorProf. Dr. Yoshihisa Yamaoka
Graduate School of Advanced Health Sciences, Saga University, Saga, 840-8502 Japan
Search for more papers by this authorTomotaka Murayama
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo, 113-0033 Japan
Search for more papers by this authorDr. Atsuya Muranaka
Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory, RIKEN, Saitama, 351-0198 Japan
Search for more papers by this authorProf. Dr. Masanobu Uchiyama
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo, 113-0033 Japan
Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory, RIKEN, Saitama, 351-0198 Japan
Search for more papers by this authorDr. Shigeki Mori
Advanced Research Support Center, Ehime University, Matsuyama, 790-8577 Japan
Search for more papers by this authorDr. Yuhsuke Yasutake
Graduate School of Arts and Sciences, The University of Tokyo, Tokyo, 153-8902 Japan
Search for more papers by this authorProf. Dr. Susumu Fukatsu
Graduate School of Arts and Sciences, The University of Tokyo, Tokyo, 153-8902 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Dongho Kim
Department of Chemistry and Spectroscopy for Functional π-Electronic Systems, Yonsei University, Seoul, 03722 Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Hiroyuki Furuta
Department of Chemistry and Biochemistry, Graduate School of Engineering, the Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395 Japan
Search for more papers by this authorAbstract
The synthesis of organometallic complexes of modified 26π-conjugated hexaphyrins with absorption and emission capabilities in the third near-infrared region (NIR-III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis-PdII and bis-PtII complexes of hexaphyrin via N-confusion modification led to substantial metal dπ–pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO–LUMO energy gap. A remarkable long-wavelength shift of the lowest S0→S1 absorption beyond 1700 nm was achieved with the bis-PtII complex, t-Pt2-3. The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t-Pt2-3 potentially useful as a NIR-III PA contrast agent. The rigid bis-PdII complexes, t-Pd2-3 and c-Pd2-3, are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR-III-emissive and photoacoustic-response capabilities.
Conflict of interest
The authors declare no conflict of interest.
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References
- 1S. Saito, A. Osuka, Angew. Chem. Int. Ed. 2011, 50, 4342–4373; Angew. Chem. 2011, 123, 4432–4464.
- 2B. Szyszko, M. J. Biåek, E. Pacholska-Dudziak, L. Latos-Grazyński, Chem. Rev. 2017, 117, 2839–2909.
- 3Z. S. Yoon, J. H. Kwon, M. C. Yoon, M. K. Koh, S. B. Noh, J. L. Sessler, J. T. Lee, D. Seidel, A. Aguilar, S. Shimizu, M. Suzuki, A. Osuka, D. Kim, J. Am. Chem. Soc. 2006, 128, 14128–14134.
- 4P. J. Boul, D. G. Cho, G. M. A. Rahman, M. Marquez, Z. Ou, K. M. Kadish, D. M. Guldi, J. L. Sessler, J. Am. Chem. Soc. 2007, 129, 5683–5687.
- 5J. D. Hooker, V. H. Nguyen, V. M. Taylor, D. L. Cedeño, T. D. Lash, M. A. Jones, S. M. Robledo, I. D. Vélez, Photochem. Photobiol. 2012, 88, 194–200.
- 6Z. Tian, S. Dai, D. Jiang, ACS Appl. Mater. Interfaces 2015, 7, 13073–13079.
- 7Z. Zhang, D. S. Kim, C. Y. Lin, H. Zhang, A. D. Lammer, V. M. Lynch, I. Popov, O. S. Miljanić, E. V. Anslyn, J. L. Sessler, J. Am. Chem. Soc. 2015, 137, 7769–7774.
- 8T. Higashino, H. Nakatsuji, R. Fukuda, H. Okamoto, H. Imai, T. Matsuda, H. Tochio, M. Shirakawa, N. V. Tkachenko, M. Hashida, T. Murakami, H. Imahori, ChemBioChem 2017, 18, 951–959.
- 9R. Paolesse, S. Nardis, D. Monti, M. Stefanelli, C. D. Natale, Chem. Rev. 2017, 117, 2517–2583.
- 10H. Ruffin, G. N. M. Boussambe, T. Roisnel, V. Dorcet, B. Boitrel, S. L. Gac, J. Am. Chem. Soc. 2017, 139, 13847–13857.
- 11G. Thiabaud, G. He, S. Sen, K. A. Shelton, W. B. Baze, L. Segura, J. Alaniz, R. M. Macias, G. Lyness, A. B. Watts, H. M. Kim, H. Lee, M. Y. Cho, K. S. Hong, R. Finch, Z. H. Siddik, J. F. Arambula, J. L. Sessler, Proc. Natl. Acad. Sci. USA 2020, 117, 7021–7029.
- 12Y. Wang, H. Kai, M. Ishida, S. Gokulnath, S. Mori, T. Murayama, A. Muranaka, M. Uchiyama, Y. Yasutake, S. Fukatsu, Y. Notsuka, Y. Yamaoka, M. Hanafusa, M. Yoshizawa, G. Kim, D. Kim, H. Furuta, J. Am. Chem. Soc. 2020, 142, 6807–6813.
- 13E. Hemmer, A. Benayas, F. Légaré, F. Vetrone, Nanoscale Horiz. 2016, 1, 168–184.
- 14A. M. Smith, M. C. Mancini, S. Nie, Nat. Nanotechnol. 2009, 4, 710–711.
- 15G. Hong, Y. Zou, A. L. Antaris, S. Diao, D. Wu, K. Cheng, X. Zhang, C. Chen, B. Liu, Y. He, J. Z. Wu, J. Yuan, B. Zhang, Z. Tao, C. Fukunaga, H. Dai, Nat. Commun. 2014, 5, 4206.
- 16A. L. Antaris, H. Chen, K. Cheng, Y. Sun, G. Hong, C. Qu, S. Diao, Z. Deng, X. Hu, B. Zhang, X. Zhang, O. K. Yaghi, Z. R. Alamparambil, X. Hong, Z. Cheng, H. Dai, Nat. Mater. 2016, 15, 235–242.
- 17A. L. Antaris, H. Chen, S. Diao, Z. Ma, Z. Zhang, S. Zhu, J. Wang, A. X. Lozano, Q. Fan, L. Chew, M. Zhu, K. Cheng, X. Hong, H. Dai, Z. Cheng, Nat. Commun. 2017, 8, 15269.
- 18Q. Yang, Z. Ma, H. Wang, B. Zhou, S. Zhu, Y. Zhong, J. Wang, H. Wan, A. Antaris, R. Ma, X. Zhang, J. Yang, X. Zhang, H. Sun, W. Liu, Y. Liang, H. Dai, Adv. Mater. 2017, 29, 1605497.
- 19H. Mori, T. Tanaka, A. Osuka, J. Mater. Chem. C 2013, 1, 2500–2519.
- 20H. Mori, T. Tanaka, S. Lee, J. M. Lim, D. Kim, A. Osuka, J. Am. Chem. Soc. 2015, 137, 2097–2106.
- 21L. Wu, F. Li, Y. Rao, B. Wen, L. Xu, M. Zhou, T. Tanaka, A. Osuka, J. Song, Angew. Chem. Int. Ed. 2019, 58, 8124–8128; Angew. Chem. 2019, 131, 8208–8212.
- 22T. Soya, W. Kim, D. Kim, A. Osuka, Chem. Eur. J. 2015, 21, 8341–8346.
- 23T. Okujima, C. Ando, S. Agrawal, H. Matsumoto, S. Mori, K. Ohara, I. Hisaki, T. Nakae, M. Takase, H. Uno, N. Kobayashi, J. Am. Chem. Soc. 2016, 138, 7540–7543.
- 24T. Tanaka, A. Osuka, Chem. Rev. 2017, 117, 2584–2640.
- 25T. Soya, H. Mori, A. Osuka, Angew. Chem. Int. Ed. 2018, 57, 15882–15886; Angew. Chem. 2018, 130, 16108–16112.
- 26Y. Tanaka, T. Yoneda, K. Furukawa, T. Koide, H. Mori, T. Tanaka, H. Shinokubo, A. Osuka, Angew. Chem. Int. Ed. 2015, 54, 10908–10911; Angew. Chem. 2015, 127, 11058–11061.
- 27X. S. Ke, Y. Hong, P. Tu, Q. He, V. M. Lynch, D. Kim, J. L. Sessler, J. Am. Chem. Soc. 2017, 139, 15232–15238.
- 28D. Shimizu, A. Osuka, Chem. Sci. 2018, 9, 1408–1423.
- 29S. Gokulnath, K. Nishimura, M. Toganoh, S. Mori, H. Furuta, Angew. Chem. Int. Ed. 2013, 52, 6940–6943; Angew. Chem. 2013, 125, 7078–7081.
- 30T. Yoneda, A. Osuka, Chem. Eur. J. 2013, 19, 7314–7318.
- 31In contrast, the hypothetical model of the corresponding bis-NiII complex of the hexaphyrin has a relatively larger HOMO–LUMO gap (Figure S1).
- 32M. Olaru, J. Beckmann, C. I. Raţ, Organometallics 2014, 33, 3012–3020.
- 33A. Srinivasan, T. Ishizuka, A. Osuka, H. Furuta, J. Am. Chem. Soc. 2003, 125, 878–879.
- 34K. Shimomura, H. Kai, Y. Nakamura, Y. Hong, S. Mori, K. Miki, K. Ohe, Y. Notsuka, Y. Yamaoka, M. Ishida, D. Kim, H. Furuta, J. Am. Chem. Soc. 2020, 142, 4429–4437.
- 35P. Pushpanandan, D. H. Won, S. Mori, Y. Yasutake, S. Fukatsu, M. Ishida, H. Furuta, Chem. Asian J. 2019, 14, 1729–1736.
- 36T. M. Krygowski, H. Szatylowicz, O. A. Stasyuk, J. Dominikowska, M. Palusiak, Chem. Rev. 2014, 114, 6383–6422.
- 37D. Geuenich, K. Hess, F. Köhler, R. Herges, Chem. Rev. 2005, 105, 3758–3772.
- 38S. Klod, E. Kleinpeter, J. Chem. Soc. Perkin Trans. 2 2001, 1893–1898.
- 39Z. Chen, C. S. Wannere, C. Corminboeuf, R. Puchta, P. v. R. Schleyer, Chem. Rev. 2005, 105, 3842–3888.
- 40W. R. Mason, Magnetic Circular Dichroism Spectroscopy, Wiley, Hoboken, 2007.
10.1002/9780470139233 Google Scholar
- 41N. Kobayashi, K. Nakai, Chem. Commun. 2007, 4077–4092.
- 42J. Mack, M. J. Stillman, N. Kobayashi, Coord. Chem. Rev. 2007, 251, 429–453.
- 43A. Muranaka, O. Matsushita, K. Yoshida, S. Mori, M. Suzuki, T. Furuyama, M. Uchiyama, A. Osuka, N. Kobayashi, Chem. Eur. J. 2009, 15, 3744–3751.
- 44J. Michl, J. Am. Chem. Soc. 1978, 100, 6801–6811.
- 45M. Bixon, J. Jortner, J. Chem. Phys. 1968, 48, 715.
- 46H. A. Frank, V. Chynwat, R. Z. B. Desamero, R. Farhoosh, J. Erickson, J. Bautista, Pure Appl. Chem. 1997, 69, 2117–2124.
- 47In general, the PdII porphyrin exhibits dual emission; fluorescence and phosphorescence. See A. Harriman, J. Chem. Soc. Faraday Trans. 2 1981, 77, 1281–1291.
- 48F. Bolze, C. P. Gros, P. D. Harvey, R. Guilard, J. Porphyrins Phthalocyanines 2001, 5, 569–574.
- 49There is no change in the emission spectra upon passing dioxygen gas into the solution because the energy level of the excited triplet state is far beyond the one of singlet oxygen (1270 nm). See Figure S22.
- 50S. Cho, Z. S. Yoon, K. S. Kim, M. C. Yoon, D. G. Cho, J. L. Sessler, D. Kim, J. Phys. Chem. Lett. 2010, 1, 895–900.
- 51S. Wang, L. Liu, Y. Fan, A. M. El-Toni, M. S. Alhoshan, D. Li, F. Zhang, Nano Lett. 2019, 19, 2418–2427.
- 52M. Zhang, J. Yue, R. Cui, Z. Ma, H. Wan, F. Wang, S. Zhu, Y. Zhou, Y. Kuang, Y. Zhong, D. Pang, H. Dai, Proc. Natl. Acad. Sci. USA 2018, 115, 6590–6595.
- 53Z. Ma, M. Zhang, J. Yue, C. Alcazar, Y. Zhong, T. C. Doyle, H. Dai, N. F. Huang, Adv. Funct. Mater. 2018, 28, 1803417.
- 54The distinct PA profiles of the bis-PdII complexes t-Pd2-3 and c-Pd2-3 were observed and relevant to the one-photon absorption spectra (Figure S25a,b).
- 55Y. Ikawa, M. Takeda, M. Suzuki, A. Osuka, H. Furuta, Chem. Commun. 2010, 46, 5689–5691.
- 56S. Diao, J. L. Blackburn, G. Hong, A. L. Antaris, J. Chang, J. Z. Wu, B. Zhang, K. Cheng, C. J. Kuo, H. Dai, Angew. Chem. Int. Ed. 2015, 54, 14758–14762; Angew. Chem. 2015, 127, 14971–14975.
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