Synthesis and spectral properties of Zr(IV) and Hf(IV) phthalocyanines with β-diketonates as axial ligands

Tomachynski, L.; Tretyakova, Iryna; Chernii, Viktor; Волков, С. В.; Kowalska, Maria; Legendziewicz, J.; Gerasymchuk, Yuriy; Radzki, S.

doi:10.1016/j.ica.2007.11.003

Cited by 32 publications

(26 citation statements)

References 22 publications

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“…63 Though the literature reports that (Pc)Zr(Cl) 2 can easily be isolated as solid product, 65 we found that careful washing of the reaction mixture yields two soluble components that were separated by color. The first dark green/brown fraction contained the unreacted material followed by a 2 nd green/blue fraction containing the dichloride salt.…”

Section: Resultsmentioning

confidence: 73%

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

et al. 2012

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Metalloporphyrin and metallophthalocyanine dyes ligating Hf(IV) and Zr(IV) ions bind to semiconductor oxide surfaces such as TiO2 via the protruding group IV metal ions. The use of oxophylic metal ions with large ionic radii that protrude from the macrocycle is a unique mode of attaching chromophores to oxide surfaces in the design of dye-sensitized solar cells (DSSCs). Our previous report on the structure and physical properties of ternary complexes wherein the Hf(IV) and Zr(IV) ions are ligated to both a porphyrinoid and to a defect site on a polyoxometalate (POM) represents a model for this new way of binding dyes to oxide surfaces. The Zr(IV) and Hf(IV) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) with two ligated acetates, (TPP)Hf(OAc)2 and (TPP)Zr(OAc)2, and the corresponding metallophthalocyanine (Pc) diacetate complexes, (Pc)Hf(OAc)2 and (Pc)Zr(OAc)2, were evaluated as novel dyes for the fabrication of dye-sensitized solar cells. Similarly to the ternary complexes with the POM, the oxide surface replaces the acetates to affect binding. In DSSCs the Zr(IV) phthalocyanine dye performs better than the Zr(IV) porphyrin dye, and reaches an overall efficiency of ~ 1.0%. The Hf(IV) dyes are less efficient. The photophysical properties of these complexes in solution suggested energetically favorable injection of electrons into the conduction band of TiO2 semiconductor nanoparticles, as well as a good band gap match with I3−/I− pair in liquid 1-butyl-3-methyl imidazolium iodide. The combination of blue absorbing TPP with the red absorbing Pc complexes can increase the absorbance of solar light in the device; however, the overall conversion efficiency of DSSCs using TiO2 nanoparticles treated with a mixture of both Zr(IV) complexes is comparable, but not greater than, the single (Pc)Zr. Thus, surface bound (TPP)Zr increases the absorbance in blue region of the spectra, but at the cost of diminished absorbance in the red in this DSSC architecture.

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Section: Resultsmentioning

confidence: 73%

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

et al. 2012

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“…[17,24] Absolute dichloromethane (CH 2 Cl 2 ) was used as received without further purification. High purity N 2 from Trigas was used to deoxygenate the solution before each electrochemical experiment.…”

Section: Chemicalsmentioning

confidence: 99%

“…[15][16][17][18][19][20][21][22][23][24][25][26][27] Metallophthalocyanines in which the central atom has a valence of three or more are known to possess one or two out of plane axial ligands. [28][29][30][31] We recently reported the synthesis of zirconium and hafnium phthalocyanine complexes with various β-diketones and polyphenols which were made by replacing the two Cl -ions of the dichloro(phthalocyanine) complexes with organic ligands [17,23,24,27] and this was followed by a preliminary electrochemical study on some of these compounds. [32] The present work is a continuation of these studies and involves the electrochemical and spectroelectrochemical characterization of fourteen related Zr IV and Hf IV derivatives whose structures are shown in Chart 1.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry and spectroelectrochemistry of zirconium(IV) and hafnium(IV) phthalocyanines with b-diketone axial ligands

Ou¹,

Zhan²,

Tomachynski³

et al. 2011

MHC

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“…16 The reduction of PcMg in DME with trace H 2 O present yielded [K 2 (DME) 4 ] [PcMg(OH)], in which the Pc 3− anion was structurally characterized. 23 As a comparison to the Nb-system, we targeted the synthesis of analogous PcZr(IV) systems [24][25][26][27][28][29][30] for reduction. 23 As a comparison to the Nb-system, we targeted the synthesis of analogous PcZr(IV) systems [24][25][26][27][28][29][30] for reduction.…”

Section: Introductionmentioning

confidence: 99%

Reducing zirconium(iv) phthalocyanines and the structure of a Pc⁴⁻Zr complex

et al. 2015

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The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (; Pc(x-) = phthalocyaninato(x-)) and its reduction products are described. X-ray analysis of (crystallized from hot 1-chloronaphthalene) reveals that is a chloride-bridged dimer [PcZrCl]2(μ-Cl)2 in the solid-state; 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 to generate Pc(3-)-containing species, as indicated by visible Q-band spectral changes (from λmax = 686 for to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted (1)H NMR resonances consistent with the presence of a Pc-radical anion. Addition of two equivalents of KEt3BH to generated Pc(4-)-containing species, confirmed by a shift in λmax to 522 nm and upfield-shifted (1)H NMR peaks relative to . Reaction of 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 Pc(4-)Zr(LiCl)1.5(DME)3, of the form [LiCl(DME)4]0.5[Pc(4-)ZrClLi(DME)] was structurally characterized, illustrating partial bond localization in the Pc(4-) ring, which also adopts a saddle-shape vs. the more typical dome-configuration found in . This represents a rare example of an isolated and structurally characterized Pc(4-) complex.

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Synthesis and spectral properties of Zr(IV) and Hf(IV) phthalocyanines with β-diketonates as axial ligands

Cited by 32 publications

References 22 publications

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Electrochemistry and spectroelectrochemistry of zirconium(IV) and hafnium(IV) phthalocyanines with b-diketone axial ligands

Reducing zirconium(iv) phthalocyanines and the structure of a Pc⁴⁻Zr complex

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Synthesis and spectral properties of Zr(IV) and Hf(IV) phthalocyanines with β-diketonates as axial ligands

Cited by 32 publications

References 22 publications

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Zirconium(IV) and Hafnium(IV) Porphyrin and Phthalocyanine Complexes as New Dyes for Solar Cell Devices

Electrochemistry and spectroelectrochemistry of zirconium(IV) and hafnium(IV) phthalocyanines with b-diketone axial ligands

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