Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury

Chidawanyika, Wadzanai; Ogunsipe, Abimbola; Nyokong, Tebello

doi:10.1039/b615663k

Cited by 56 publications

(23 citation statements)

References 30 publications

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“…The quaternized peripherally tetra-substituted zinc Pc complex (10) showed highest F D value than other studied quaternized zinc Pc complexes in water. Singlet oxygen quantum yield (F D ) values of all employed mercaptopyridine substituted zinc Pc complexes were higher (ranging from 0.51e0.86 in DMSO), than those of their corresponding pyridyloxy substituted zinc Pc complexes in literature that ranged from 0.06e0.46 [51,58]. The F D values, found in this study, are similar to those of Cd(II), Hg(II), Ga(III), In(III), Si(IV) and [33].…”

Section: Singlet Oxygen Quantum Yieldsmentioning

confidence: 82%

Water-soluble quaternized mercaptopyridine-substituted zinc-phthalocyanines: Synthesis, photophysical, photochemical and bovine serum albumin binding properties

et al. 2011

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Section: Singlet Oxygen Quantum Yieldsmentioning

confidence: 82%

Water-soluble quaternized mercaptopyridine-substituted zinc-phthalocyanines: Synthesis, photophysical, photochemical and bovine serum albumin binding properties

et al. 2011

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“…In principle, the data presented in Table 3 does not indicate a favorable intersystem crossing between S 1 and the adjacent triplet state, in apparent contradiction to the ZnPc photophysical behavior given by the expressive triplet (Φ T = 0.65) and singlet oxygen (Φ D = 0.67) quantum yields in DMSO. 16 This should occur mainly due to the spin-orbit coupling induced by Zn 2+ at the center of the macrocycle. 16 The experimentally evidenced weak p,p* transition with a partial contribution of n,p* transition, 24,27,47 near the Q band, in combination with the spin-orbit coupling, also should favor the intersystem crossing, resulting in the population of T 1 with a good probability.…”

Section: Phosphorescencementioning

confidence: 99%

“…16 This should occur mainly due to the spin-orbit coupling induced by Zn 2+ at the center of the macrocycle. 16 The experimentally evidenced weak p,p* transition with a partial contribution of n,p* transition, 24,27,47 near the Q band, in combination with the spin-orbit coupling, also should favor the intersystem crossing, resulting in the population of T 1 with a good probability. The p,p* nature of T 2 and T 1 warrants a fast internal conversion between these states and a long-lived T 1 state, capable to favor the efficient sensitization of molecular oxygen to singlet oxygen by energy transfer (Φ D = 0.67 in DMSO).…”

Section: Phosphorescencementioning

confidence: 99%

“…The p,p* nature of T 2 and T 1 warrants a fast internal conversion between these states and a long-lived T 1 state, capable to favor the efficient sensitization of molecular oxygen to singlet oxygen by energy transfer (Φ D = 0.67 in DMSO). 16 The lowest triplet state ( (1) 3 B 2u -D 2h symmetry) was optimized with the use of two methods, for both gas phase and in DMSO as solvent. The first employed B3LYP/6-31G(d) in an TD-DFT unrestricted approach, and the other using B3LYP/6-311+G(d,p), both using as starting point the S 1 optimized geometry.…”

Section: Phosphorescencementioning

confidence: 99%

“…13 The photophysics of ZnPc has been extensively studied by many researchers. [14][15][16] Fluorescence quantum yields and other parameters have been reported in different solvents. 14 Absorption and photoluminescence of ZnPc have been studied with the use of a great variety of experimental techniques.…”

Section: Introductionmentioning

confidence: 99%

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Photophysics and spectroscopic properties of zinc phthalocyanine revisited using quantum chemistry

Ueno¹,

Jayme²,

Silva³

et al. 2012

J. Braz. Chem. Soc.

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Este estudo fornece uma avaliação teórica do comportamento fotofísico da ftalocianina de zinco (FtZn) usando teoria do funcional da densidade (DFT) e a sua abordagem dependente do tempo (TD-DFT), baseado na combinação do funcional híbrido B3LYP e o conjunto de base 6-311+G(d,p). A influência da solvatação foi estimada utilizando o método IEFPCM (modelo do contínuo polarizável) e considerando DMSO (dimetilsulfóxido) como solvente. Os espectros de absorção simulados foram baseados no cálculo dos primeiros 40 estados excitados sendo que os oito picos mais intensos podem ser atribuídos às bandas Q e Soret (B). Comprimento de onda de emissão de fluorescência e tempo de vida radiativo foram calculados utilizando a abordagem TD-DFT e comparados com dados experimentais. O fenômeno de cruzamento intersistema (CIS) da FtZn foi atribuído ao acoplamento spin-órbita induzida pelo Zn 2+ pelo fato dos estados singlete e triplete adjacentes possuirem a mesma simetria orbital. Os dados de fosforescência em fase gasosa também foram comparados.This study provides a theoretical evaluation of the photophysical behavior of zinc phthalocyanine (ZnPc) using density functional theory (DFT) and its time-dependent (TD-DFT) approach, based on the combination of the B3LYP hybrid functional and the 6-311+G(d,p) basis set. The influence of solvation was estimated using IEFPCM (integral equation formalism approach of polarizable continuum model) considering DMSO (dimethyl sulfoxide) as solvent. The simulated absorption spectra were based in the calculation of the first 40 excited states being that the eight most intense peaks could be assigned to the Q and Soret (B) bands. Fluorescence emission wavelength and radiative lifetime were calculated using the TD-DFT approach and compared to experimental data. The ZnPc intersystem crossing (ISC) phenomena was attributed to spin-orbit coupling induced by Zn 2+ since the adjacent singlet and triplet states have the same orbital symmetry. The phosphorescence data in gas phase were also compared.

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Oligomeric Cadmium–Phthalocyanine Complexes: Novel Supramolecular Free Radical Structures

Chambrier

White

Cook

2007

Chemistry A European J

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Certain cadmium-metallated phthalocyanines give rise to EPR active triple-decker sandwich complexes containing two Cd ions and three phthalocyanine (Pc) ligands. These have been shown to form when the ligands bear either eight non- peripheral alkyl or alkenyl substituents or eight peripheral 2-ethylhexyl groups. They can be derived either from three equivalents of a cadmium phthalocyanine precursor or from a 2:1 mixture of a cadmium phthalocyanine (CdPc) and a metal-free phthalocyanine (H(2)Pc). The mode of their formation has been investigated by a series of "cross" experiments. The results indicate that the triple-decker structures are formed by a self-assembly process. This is deduced from results that show that they can disassemble and reassemble with incorporation of differently substituted ligands derived from either an H(2)Pc or CdPc. The reassembled structures in these cross experiments can contain more than one ligand that originated from either the added CdPc or, and more surprisingly, the H(2)Pc compound. Mass spectrometry has also established that higher order oligomers can be formed when steric requirements between the alkyl substituents on adjacent rings in the stack are reduced. Thus an isotopic cluster for a Cd(5)Pc(6) complex has been observed when the eight peripheral substituents are hexyl chains and tetrameric complexes are formed when two different ligands are incorporated within a stack, with one carrying substituents at the peripheral sites and the other bearing substituents at the non-peripheral sites.

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Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury

Cited by 56 publications

References 30 publications

Water-soluble quaternized mercaptopyridine-substituted zinc-phthalocyanines: Synthesis, photophysical, photochemical and bovine serum albumin binding properties

Water-soluble quaternized mercaptopyridine-substituted zinc-phthalocyanines: Synthesis, photophysical, photochemical and bovine serum albumin binding properties

Photophysics and spectroscopic properties of zinc phthalocyanine revisited using quantum chemistry

Oligomeric Cadmium–Phthalocyanine Complexes: Novel Supramolecular Free Radical Structures

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