Accepted author manuscript, 3.71 MB, PDF document
Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License
Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
<mark>Journal publication date</mark> | 30/11/2019 |
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<mark>Journal</mark> | Journal of Porphyrins and Phthalocyanines |
Issue number | 11-12 |
Volume | 23 |
Number of pages | 11 |
Pages (from-to) | 1592-1602 |
Publication Status | Published |
<mark>Original language</mark> | English |
The preparation and structural characterization of a pair of scanditun(III) phthalocyanine hydroxide complexes were achieved by reaction of PcScCl with alkali metal alkoxides, likely via hydrolysis of soluble PcSc-alkoxide intermediates. A Sc2Li2 (mu(3)-OH)(4) cubane supported by two distorted Pc rings of the form (PcSc)(2)(mu(3)-OH)(4)Li-2 (THF)(DME) was isolated from the reaction of PcScCl with (LiOPr)-Pr-i, while a simpler alkali-metal-free [Pc2Sc2(mu(2)-OH)(2)(THE)] was obtained from addition of (NaOBu)-Bu-i; both structures are reminiscent of bent metallocenes, with dihedral angles between the two Pc rings of 50.8 and 37.7 degrees respectively. A soluble PcScOH material can also be obtained directly via hydrolysis of insoluble PcScCl in approximately 95:5 THF:water. Reduction of the Pc ring of PcScCl using KC8 is reversible and generates Pc3- and Pc4--containing materials that were characterized via UV-vis spectroscopy and, where appropriate EPR and H-1 NMR spectroscopy; analogous reductions of the PcScOH-based species were irreversible. Exposure of the air-sensitive, reduced PcScCl-based species to ambient atmosphere generated PcScOH materials analogous to the direct hydrolysis route.