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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Synthesis, structures and reduction chemistry of monophthalocyanine scandium hydroxides
AU - Ganga-Sah, Y.
AU - Tajbakhsh, E.
AU - Platel, R.H.
AU - Zhou, W.
AU - Leznoff, D.B.
PY - 2019/11/30
Y1 - 2019/11/30
N2 - 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.
AB - 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.
KW - scandium
KW - phthalocyanine
KW - hydroxides
KW - crystal structures
KW - ring-reduced phthalocyanines
U2 - 10.1142/S1088424619501992
DO - 10.1142/S1088424619501992
M3 - Journal article
VL - 23
SP - 1592
EP - 1602
JO - Journal of Porphyrins and Phthalocyanines
JF - Journal of Porphyrins and Phthalocyanines
IS - 11-12
ER -