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Homoleptic complexes of a porphyrinatozinc(II)-2,2’:6’,2’’-terpyridine ligand

Lanzilotto, Angelo and Kuss-Petermann, Martin and Wenger, Oliver S. and Constable, Edwin C. and Housecroft, Catherine E.. (2017) Homoleptic complexes of a porphyrinatozinc(II)-2,2’:6’,2’’-terpyridine ligand. Photochemical and Photobiological Sciences, 16 (4). pp. 585-595.

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Abstract

Three homoleptic complexes containing the metalloligand 7-(4-([2,2′:6′,2′′-terpyridin]-4′-yl)phenyl)-5,10,15,20-tetraphenylporphyrinatozinc(II), 1, have been prepared. [Zn(1)2][PF6]2, [Fe(1)2][PF6]2 and [Ru(1)2][PF6]2 were characterized by 1H and 13C NMR spectroscopy and mass spectrometry, and the electrochemical and photophysical properties of the complexes have been investigated. In solution, each complex undergoes two reversible porphyrin-centred oxidation processes, with an additional reversible metal-centred oxidation for [Fe(1)2][PF6]2 and [Ru(1)2][PF6]2. Solution absorption spectra are dominated by the Soret and Q bands of the metalloligand 1. Spectroelectrochemical data for the complexes are presented. The results of a nanosecond transient absorption spectroscopic investigation of [Zn(1)2][PF6]2, [Fe(1)2][PF6]2 and [Ru(1)2][PF6]2 are presented. For [Zn(1)2][PF6]2, S1 excitation leads to an efficient intersystem-crossing to the T1 state, whilst for [Fe(1)2][PF6]2, excitation of the 1MLCT transition is followed by fast deactivation to the 3MC state followed by thermal decay to the ground state. Excitation of the 1MLCT transition of [Ru(1)2][PF6]2 results in an intersystem crossing to 3MLCT; triplet-to-triplet energy transfer occurs giving the [Zn(TPP)] T1 state which regenerates the ground state of the complex.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Wenger, Oliver and Lanzilotto, Angelo and Kuss-Petermann, Martin
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
ISSN:1474-905X
e-ISSN:1474-9092
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:23 Feb 2018 14:36
Deposited On:20 Apr 2017 09:49

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