Nonaromatic Organonickel(II) Phototheranostics
- Yuhang YaoYuhang YaoBeijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaMore by Yuhang Yao
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- Guangliu RanGuangliu RanCenter for Advanced Quantum Studies, Department of Physics and Applied Optics Beijing Area Major Laboratory, Beijing Normal University, Beijing 100875, P. R. ChinaMore by Guangliu Ran
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- Chun-Liang HouChun-Liang HouCenter of Materials Science and Optoelectronics Engineering, College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, P. R. ChinaMore by Chun-Liang Hou
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- Ruijing ZhangRuijing ZhangBeijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaMore by Ruijing Zhang
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- Daniel N. MangelDaniel N. MangelDepartment of Chemistry, The University of Texas at Austin, Austin, Texas 78712-1224, United StatesMore by Daniel N. Mangel
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- Zi-Shu YangZi-Shu YangBeijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaMore by Zi-Shu Yang
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- Mengliang ZhuMengliang ZhuBeijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaMore by Mengliang Zhu
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- Wenkai Zhang*Wenkai Zhang*Email: [email protected]Center for Advanced Quantum Studies, Department of Physics and Applied Optics Beijing Area Major Laboratory, Beijing Normal University, Beijing 100875, P. R. ChinaMore by Wenkai Zhang
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- Jing Zhang*Jing Zhang*Email: [email protected]Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, P. R. ChinaMore by Jing Zhang
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- Jonathan L. Sessler*Jonathan L. Sessler*Email: [email protected]Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712-1224, United StatesMore by Jonathan L. Sessler
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- Song GaoSong GaoBeijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaChemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, P. R. ChinaThe Institute of Spin Science and Technology, South China University of Technology, Guangzhou 510641, P. R. ChinaMore by Song Gao
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- Jun-Long Zhang*Jun-Long Zhang*Email: [email protected]Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaChemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, P. R. ChinaMore by Jun-Long Zhang
Abstract
Earth-abundant metal-based theranostics, agents that integrate diagnostic and therapeutic functions within the same molecule, may hold the key to the development of low-cost personalized medicines. Here, we report a set of O-linked nonaromatic benzitripyrrin (C^N^N^N) macrocyclic organonickel(II) complexes, Ni-1–4, containing strong σ-donating M–C bonds. Complexes Ni-1–4 are characterized by a square-planar coordination geometry as inferred from the structural studies of Ni-1. They integrate photothermal therapy, photothermal imaging, and photoacoustic imaging (PAI) within one system. This makes them attractive as potential phototheranostics. Relative to traditional Ni(II) porphyrins, such as F20TPP (tetrapentafluorophenylporphyrin), the lowest energy absorption of Ni-1 is shifted into the near infrared region, presumably as a consequence of Ni–C bonding. Ultrafast transient absorption spectroscopy combined with theoretical calculations revealed that, upon photoexcitation, a higher population of ligand-centered and 3MLCT states is seen in Ni-1 relative to NiTPBP (TPBP = 6,11,16,21-tetraphenylbenziporphyrin). Encapsulating Ni-1 in 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) afforded nanoparticles, Ni-1@DSPE, displaying red-shifted absorption features, as well as good photothermal conversion efficiency (∼45%) in aqueous media. Proof-of-principle experiments involving thrombus treatment were carried out both in vitro and in vivo. It was found that Ni-1@DSPE in combination with 785 nm photo-irradiation for 3 min (0.3 W/cm2) proved successful in removing blood clots from a mouse thrombus model as monitored by photoacoustic imaging (PAI). The present work highlights the promise of organonickel(II) complexes as potential theranostics and the benefits that can accrue from manipulating the excited-state features of early transition-metal complexes via, for example, interrupting π-conjugation pathways.
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