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Title
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Synthesis and characterization of heteroleptic rare earth double-decker complexes involving tetradiazepinoporphyrazine and phthalocyanine macrocycles
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Author
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Abstract
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| Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates ((Bu)PcLn(acac), 1a-c, Ln = Lu (a), Eu (b), La (c)) with a tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand ((tBuPh)DzPzH(2), 2) produced sandwich compounds ((tBuPh)DzPz)Ln(Pc-Bu) (3a-c), which represent the first heteroleptic double-deckers incorporating both Pc and DzPz decks. A combination of high-resolution mass spectrometry, UV-Vis/NIR, MCD, and H-1 NMR spectroscopy, and square-wave voltammetry provided unambiguous characterization of target complexes 3 indicating that their spectral and electrochemical properties are generally intermediate with respect to their homoleptic relatives. Based on the data of solution-state H-1-H-1 NMR (COSY, NOESY) correlation spectroscopy supported by DFT calculations, a dimerization tendency of compounds 3 proportional to the Ln(iii) ion size was found. The spectroelectrochemical study of 3 and the corresponding homoleptic double-deckers revealed a pronounced tendency to aggregation of the one-electron oxidized forms of DzPz-containing double-decker complexes compared to homoleptic Pc(2)Ln compounds. |
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Language
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English
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Source (journal)
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Dalton Transactions : an international journal of inorganic chemistry / Royal Society of Chemistry [London] - Cambridge, 2003, currens
Journal of the Chemical Society : Dalton transactions. - London, 1972 - 1999
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Publication
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Cambridge
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Royal soc chemistry
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2021
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ISSN
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1477-9226
[print]
1477-9234
[online]
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DOI
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10.1039/D1DT00088H
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Volume/pages
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50
:18
(2021)
, p. 6245-6255
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ISI
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000641283000001
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Pubmed ID
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33876177
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Full text (Publisher's DOI)
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