Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(<scp>III</scp>) Complexes

Zhu, Peihua; Lu, Fanli; Pan, Na; Arnold, Dennis P.; Zhang, Shuyong; Jiang, Jianzhuang

doi:10.1002/ejic.200300509

Cited by 100 publications

(114 citation statements)

References 43 publications

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“…The electrochemical behavior of all the newly prepared tetrapyrrole arrays 7-9 together with 1 and [Eu(Pc) 2 ] [22] was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH 2 Cl 2 . The heteroarrays displayed up to four oxidations and up to six reductions within the electrochemical window of CH 2 Cl 2 under ambient conditions.…”

Section: Electrochemical Propertiesmentioning

confidence: 99%

Porphyrin‐Appended Europium(III) Bis(phthalocyaninato) Complexes: Synthesis, Characterization, and Photophysical Properties

Bian

Chen

Wang

et al. 2007

Chemistry A European J

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Mixed cyclization of 3-mono-, 4-mono-, or 4,5-di(porphyrinated) phthalonitrile compounds 2, 3, or 6 and unsubstituted phthalonitrile with the half-sandwich complex [EuIII(acac)(Pc)] (Pc=phthalocyaninate, acac=acetylacetonate) as the template in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol afforded novel porphyrin-appended europium(III) bis(phthalocyaninato) complexes 7-9 in 30-40% yield. These mixed tetrapyrrole triads and tetrad were spectroscopically and electrochemically characterized and their photophysical properties were also investigated with steady-state and transient spectroscopic methods. It has been found that the fluorescence of the porphyrin moiety is quenched effectively by the double-decker unit through an intramolecular photoinduced electron-transfer process, which takes place in several hundred femtoseconds, while the recombination of the charge-separated state occurs in several picoseconds. By using different phthalocyanines containing different numbers of porphyrin substituents at the peripheral or nonperipheral position(s) of the ligand, while the other unsubstituted phthalocyanine remains unchanged in these double-deckers, the effects of the number and the position of the porphyrin substituents on these photophysical processes were also examined.

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Section: Electrochemical Propertiesmentioning

confidence: 99%

Porphyrin‐Appended Europium(III) Bis(phthalocyaninato) Complexes: Synthesis, Characterization, and Photophysical Properties

Bian

Chen

Wang

et al. 2007

Chemistry A European J

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“…Compared with the electrochemical data of the corresponding [M III (Pc) 2 ], [19] the oxidation potentials of ). This also shows that the p-p interaction is weaker for these bis(tetra-a-substituted phthalocyaninato) rare-earth complexes.…”

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confidence: 99%

Studies of “Pinwheel‐Like” Bis[1,8,15,22‐tetrakis(3‐pentyloxy)phthalocyaninato] Rare Earth(III) Double‐Decker Complexes

Wang

Bian

et al. 2005

Chemistry A European J

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Homoleptic bis(phthalocyaninato) rare-earth double-deckers complexes [M(III)[Pc(alpha-OC5H11)4]2] (M = Eu, Y, Lu; Pc(alpha-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate) have been prepared by treating the metal-free phthalocyanine H2Pc(alpha-OC5H11)4 with the corresponding M(acac)3.nH2O (acac = acetylacetonate) in refluxing n-octanol. Due to the C4h symmetry of the Pc(alpha-OC5H11)4 ligand and the double-decker structure, all the reactions give a mixture of two stereoisomers with C4h and D4 symmetry. The former isomer, which is a major product, can be partially separated by recrystallization due to its higher crystallinity. The molecular structure of the major isomer of the Y analogue has been determined by single-crystal X-ray diffraction analysis. The metal center is eight-coordinate bound to the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. Such an arrangement leads to an interesting pinwheel structure when viewed along the C4 axis, which assumes a very unusual S8 symmetry. The major isomers of all these double-deckers have also been characterized with a wide range of spectroscopic methods. A systematic investigation of their electronic absorption and electrochemical data reveals that the pi-pi interaction between the two Pc(alpha-OC5H11)4 rings is weaker than that for the corresponding unsubstituted or beta-substituted bis(phthalocyaninato) analogues.

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“…The presented spectral parameters of oxidized forms of the complexes agree well with the literature data on the spectrophotometric titration of the double-decker complexes of praseodymium and cerium by oxidizing and reducing agents. [33] However, it turned out that solution spectra do not assume the shape described in [10,19,26,[32][33][34] characteristic for chemically reduced forms of bisphthalocyaninates under mentioned conditions at reduction potentials. It is well-known, that the absorbance band around 500 nm, which corresponds to the presence of unpaired electron in the complex, and Q-band of the initial form of the complex disappear upon chemical reduction.…”

Section: Resultsmentioning

confidence: 99%

The Role of Oxygen in Electrochemical Reduction of Double-Decker Phthalocyaninates of Lanthanides

Selektor¹,

Shokurov²,

Ревина³

et al. 2015

MHC

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Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(III) Complexes

Cited by 100 publications

References 43 publications

Porphyrin‐Appended Europium(III) Bis(phthalocyaninato) Complexes: Synthesis, Characterization, and Photophysical Properties

Porphyrin‐Appended Europium(III) Bis(phthalocyaninato) Complexes: Synthesis, Characterization, and Photophysical Properties

Studies of “Pinwheel‐Like” Bis[1,8,15,22‐tetrakis(3‐pentyloxy)phthalocyaninato] Rare Earth(III) Double‐Decker Complexes

The Role of Oxygen in Electrochemical Reduction of Double-Decker Phthalocyaninates of Lanthanides

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