Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex

Wen Zhou, Rachel H. Platel, Thiago Teixeira Tasso, Taniyuki Furuyama, Nagao Kobayashi, Daniel B. Leznoff

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26 Citations (Scopus)

Abstract

The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (1; Pcx- = phthalocyaninatox-) and its reduction products are described. X-ray analysis of 1 (crystallized from hot 1-chloronaphthalene) reveals that 1 is a chloride-bridged dimer [PcZrCl]2(μ-Cl)2 in the solid-state; 1 was also characterized by UV-vis/MCD spectroscopy and cyclic voltammetry, which indicated reduction potentials at -0.55, -0.95 and -1.28 V. Although attempts to access these Pc-ring reduced species with KC8 led to mixtures of reduced products due to the insolubility of both starting materials, one equivalent of the reducing agent KEt3BH reacted with 1 to generate Pc3--containing species, as indicated by visible Q-band spectral changes (from λmax = 686 for 1 to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted 1H NMR resonances consistent with the presence of a Pc-radical anion. Addition of two equivalents of KEt3BH to 1 generated Pc4--containing species, confirmed by a shift in λmax to 522 nm and upfield-shifted 1H NMR peaks relative to 1. Reaction of 1 with one and two equivalents of LiCp∗ did not generate Cp∗-substituted products but also effected reduction to analogous Pc3- and Pc4- species. This latter material, the air-sensitive ring di-reduced "ate"-complex Pc4-Zr(LiCl)1.5(DME)3, of the form [LiCl(DME)4]0.5[Pc4-ZrClLi(DME)] was structurally characterized, illustrating partial bond localization in the Pc4- ring, which also adopts a saddle-shape vs. the more typical dome-configuration found in 1. This represents a rare example of an isolated and structurally characterized Pc4- complex.

Original languageEnglish
Pages (from-to)13955-13961
Number of pages7
JournalDalton Transactions
Volume44
Issue number31
DOIs
Publication statusPublished - 2015 Jun 25

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Zhou, W., Platel, R. H., Teixeira Tasso, T., Furuyama, T., Kobayashi, N., & Leznoff, D. B. (2015). Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex. Dalton Transactions, 44(31), 13955-13961. https://doi.org/10.1039/c5dt01778e