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Synthesis, structures and reduction chemistry of monophthalocyanine scandium hydroxides

Yumeela Ganga-Sah

Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C, V5A 1S6, Canada

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Elahe Tajbakhsh

Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C, V5A 1S6, Canada

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Rachel H. Platel

Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C, V5A 1S6, Canada

Current address: Department of Chemistry, Lancaster University, Lancaster, UK.

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Wen Zhou

Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C, V5A 1S6, Canada

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, and

Daniel B. Leznoff

Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C, V5A 1S6, Canada

E-mail Address: [email protected]

Corresponding author, tel.: 778-782-4887, fax 778-782-3765.

SPP full member in good standing.

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https://doi.org/10.1142/S1088424619501992Cited by:3

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Abstract

The preparation and structural characterization of a pair of scandium(III) phthalocyanine hydroxide complexes were achieved by reaction of PcScCl with alkali metal alkoxides, likely via hydrolysis of soluble PcSc-alkoxide intermediates. A Sc $_{2}$ Li $_{2} (μ_{3}$ -OH) $_{4}$ cubane supported by two distorted Pc rings of the form (PcSc) $_{2} (μ_{3}$ -OH) $_{4}$ Li $_{2}$ (THF)(DME) was isolated from the reaction of PcScCl with LiO $^{i}$ Pr, while a simpler alkali-metal-free [Pc $_{2}$ Sc $_{2} (μ_{2}$ -OH) $_{2}$ (THF)] was obtained from addition of NaO $^{t}$ Bu; both structures are reminiscent of bent metallocenes, with dihedral angles between the two Pc rings of 50.8 and 37.7 $^{\circ}$ 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 KC $_{8}$ is reversible and generates Pc $^{3-}$ and Pc $^{4-}$ -containing materials that were characterized via UV-vis spectroscopy and, where appropriate EPR and $^{1}$ H 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.

This paper is part of the 2019 Women in Porphyrin Science special issue.

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Received 16 October 2019

Accepted 24 November 2019

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Synthesis, structures and reduction chemistry of monophthalocyanine scandium hydroxides

Abstract

References

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