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Ultrafast Dynamics of Manganese(III), Manganese(II), and Free-Base Bacteriochlorin: Is There Time for Photochemistry?

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Luzitin SA, Ed. Bluepharma, S. Martinho do Bispo, 3045-016 Coimbra, Portugal
Chemistry Department, University of Coimbra, 3004-535 Coimbra, Portugal
§ LaserLeap SA, IPN, R. Pedro Nunes, 3030-199 Coimbra, Portugal
*E-mail: [email protected]. Phone: (+)351 239 852 808. Fax: (+)351 239 827 703.
Cite this: Inorg. Chem. 2017, 56, 5, 2677-2689
Publication Date (Web):February 16, 2017
https://doi.org/10.1021/acs.inorgchem.6b02871
Copyright © 2017 American Chemical Society
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Abstract

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Manganese(III) and manganese(II) complexes of halogenated sulfonamide tetraphenylbacteriochlorins were prepared for the first time via a transmetalation reaction and shown to be stable at room temperature. The behavior of the electronic states of the paramagnetic complexes is remarkably different from those of the metal-free bacteriochlorins or diamagnetic metallobacteriochlorins. The Mn3+ complex exhibits eight electronic transitions between different states from 300 to 1100 nm, with a very prominent band (molar absorption coefficient of ca. 50000 M–1 cm–1) at 829 nm. Ultrafast transient absorption showed the formation of an excited singquintet state that decays to a tripquintet state with a femtosecond lifetime. The tripquintet state decays in 5 ps, yielding a tripseptet state with a 570 ps lifetime. The electronic absorption of the Mn2+ complex more closely resembles those of diamagnetic metallobacteriochlorins, but the longest decay lifetime is only ca. 8 ps. The intense photoacoustic waves generated with near-infrared excitation suggest the use of these complexes in photoacoustic tomography.

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Cited By


This article is cited by 2 publications.

  1. Alexandre D. Silva, Carlos Serpa, Luis G. Arnaut. Photoacoustic transfection of DNA encoding GFP. Scientific Reports 2019, 9 (1) DOI: 10.1038/s41598-018-37759-1.
  2. Li-Li Wang, Su-Hong Peng, Hui Wang, Liang-Nian Ji, Hai-Yang Liu. Photophysical properties of free-base and manganese( iii ) N-confused porphyrins. Physical Chemistry Chemical Physics 2018, 20 (30) , 20141-20148. DOI: 10.1039/C8CP02223B.

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