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

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Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex. / Zhou, Wen; Platel, Rachel H.; Tasso, Thiago Teixeira; Furuyama, Taniyuki; Kobayashi, Nagao; Leznoff, Daniel B.

In: Dalton Transactions, Vol. 44, No. 31, 21.08.2015, p. 13955-13961.

Research output: Contribution to journalJournal article

Harvard

Zhou, W, Platel, RH, Tasso, TT, Furuyama, T, Kobayashi, N & Leznoff, DB 2015, 'Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex', Dalton Transactions, vol. 44, no. 31, pp. 13955-13961. https://doi.org/10.1039/c5dt01778e

APA

Zhou, W., Platel, R. H., Tasso, T. 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

Vancouver

Zhou W, Platel RH, Tasso TT, Furuyama T, Kobayashi N, Leznoff DB. Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex. Dalton Transactions. 2015 Aug 21;44(31):13955-13961. https://doi.org/10.1039/c5dt01778e

Author

Zhou, Wen ; Platel, Rachel H. ; Tasso, Thiago Teixeira ; Furuyama, Taniyuki ; Kobayashi, Nagao ; Leznoff, Daniel B. / Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex. In: Dalton Transactions. 2015 ; Vol. 44, No. 31. pp. 13955-13961.

Bibtex

@article{f58ba9daa47649f58f8910c08936c49a,
title = "Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex",
abstract = "The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (1; Pcx- = phthalocyaninato(x-)) 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)(mu-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 lambda(max) = 686 for 1 to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted H-1 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 lambda(max) to 522 nm and upfield-shifted H-1 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 Pc-3 and Pc-4 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.",
keywords = "METAL-FREE PHTHALOCYANINES, X-RAY-STRUCTURE, MAGNETIC-PROPERTIES, RADICAL-ANIONS, ELECTRONIC-STRUCTURE, MOLECULAR-STRUCTURE, CRYSTAL-STRUCTURES, OPTICAL-SPECTRA, ELECTROCHEMISTRY, SPECTROSCOPY",
author = "Wen Zhou and Platel, {Rachel H.} and Tasso, {Thiago Teixeira} and Taniyuki Furuyama and Nagao Kobayashi and Leznoff, {Daniel B.}",
year = "2015",
month = aug
day = "21",
doi = "10.1039/c5dt01778e",
language = "English",
volume = "44",
pages = "13955--13961",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "31",

}

RIS

TY - JOUR

T1 - Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex

AU - Zhou, Wen

AU - Platel, Rachel H.

AU - Tasso, Thiago Teixeira

AU - Furuyama, Taniyuki

AU - Kobayashi, Nagao

AU - Leznoff, Daniel B.

PY - 2015/8/21

Y1 - 2015/8/21

N2 - The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (1; Pcx- = phthalocyaninato(x-)) 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)(mu-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 lambda(max) = 686 for 1 to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted H-1 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 lambda(max) to 522 nm and upfield-shifted H-1 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 Pc-3 and Pc-4 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.

AB - The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (1; Pcx- = phthalocyaninato(x-)) 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)(mu-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 lambda(max) = 686 for 1 to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted H-1 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 lambda(max) to 522 nm and upfield-shifted H-1 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 Pc-3 and Pc-4 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.

KW - METAL-FREE PHTHALOCYANINES

KW - X-RAY-STRUCTURE

KW - MAGNETIC-PROPERTIES

KW - RADICAL-ANIONS

KW - ELECTRONIC-STRUCTURE

KW - MOLECULAR-STRUCTURE

KW - CRYSTAL-STRUCTURES

KW - OPTICAL-SPECTRA

KW - ELECTROCHEMISTRY

KW - SPECTROSCOPY

U2 - 10.1039/c5dt01778e

DO - 10.1039/c5dt01778e

M3 - Journal article

VL - 44

SP - 13955

EP - 13961

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 31

ER -