Modulation of the electronic and spectroscopic properties of Zn(ii) phthalocyanines by their substitution pattern

Topal, Sevinç Zehra; İşçi, Ümit; Kumru, Ufuk; Atílla, Devrim; Gürek, Ayşe Gül; Hirel, Catherine; Durmuş, Mahmut; Tommasino, Jean Bernard; Luneau, Dominique; Berber, Savaş; Dumoulin, Fabienne; Ahsen, Vefa

doi:10.1039/c3dt53410c

Cited by 85 publications

(66 citation statements)

References 64 publications

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“…Such lifetimes are in agreement with the ones reported for ZnPcs dissolved in chloroform [16] and are close to the one reported for B4 dissolved in THF [17]. Once the fluorescence lifetime and quantum yields are determined, one could estimate the radiative rate = ϕ / from all samples dissolved in chloroform.…”

Section: Fluorescence Lifetimes (Time-resolved Measurements)supporting

confidence: 77%

“…The sharp and single Q-bands confirm that phthalocyanines dissolved in chloroform are not aggregated at the used concentration. The absorption spectrum for B4 is similar to the one reported in [17], in which the solvent was THF, with a polarity index similar to chloroform. In the case of the low symmetrical AB3 and ABAB, the Q 00 band does not present a significant split (shoulder at 684 for ABAB).…”

Section: Ground State Electronic Absorption and Steady-state Fluorescsupporting

confidence: 69%

“…This quantity will be needed to describe the population dynamics observed in ZnPcs excited states employing a rate equation model. The fluorescence spectra displays a single emission band that ends at approximately 800 nm, a behavior similar to the ones already reported in the literature [16,17]. …”

Section: Ground State Electronic Absorption and Steady-state Fluorescsupporting

confidence: 68%

“…By reducing the hexylsulfonyl groups, the charge density on the ring decreases, increasing the radiative decay rates and the fluorescence quantum yield [4]. Topal and coworkers [17] observed a similar behavior when they compared B4 with an almost identical phthalocyanine; the only difference was the replacement of the sulfur atoms by oxygen ones. Due to the lower electron-donating strength caused by the replacement of the sulfur, the fluorescence quantum yield was significantly increased from 13% to 19%.…”

Section: Fluorescence Quantum Yield Measurementsmentioning

confidence: 56%

“…Zinc phthalocyanines [16,17] present interesting fluorescence properties, high triplet yield, long lifetime and optical nonlinearities [18][19][20][21], such as large nonlinear absorption due to the intense reverse saturable absorption [22] (RSA), which led us to design 2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyaninato)zinc (B4), (2,3,9,10,16,17 hexakis(hexylthio)phthalocyaninato)zinc Herein, the synthesis and characterization of B4, AB3 and ABAB are reported, as well as their photophysical and nonlinear optical properties. For the analysis of optical nonlinearities dynamics and excited states' properties, single pulse [23] and pulse trains [24] Z-scan techniques were used, both at 532 nm.…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of the Zn(II)Phthalocyanines’ Photochemical Reactions Depending on the Number of Substituents and Geometry

et al. 2016

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Abstract:In this work, the synthesis and the nonlinear absorption and population dynamics investigation of a series of zinc phthalocyanines (ZnPcs) dissolved in chloroform are reported. In order to determine the relevant spectroscopic parameters, such as absorption cross-sections of singlet and triplet excited states, fluorescence relaxation times, intersystem crossing, radiative decay and internal conversion, different optical and spectroscopic techniques were used. By single pulse and pulse train Z-scan techniques, respectively, singlet and triplet excited states' absorption cross-section were determined at 532 nm. Furthermore, the intersystem crossing time was obtained by using both techniques combined with the fluorescence lifetime determined by time-resolved fluorescence. The radiative and internal conversion rates were determined from the fluorescence quantum yield of the samples. Such spectroscopy parameters are fundamental for selecting photosensitizers used in photodynamic therapy, as well as for many other applications.

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Section: Fluorescence Lifetimes (Time-resolved Measurements)supporting

confidence: 77%

Section: Ground State Electronic Absorption and Steady-state Fluorescsupporting

confidence: 69%

Section: Ground State Electronic Absorption and Steady-state Fluorescsupporting

confidence: 68%

Section: Fluorescence Quantum Yield Measurementsmentioning

confidence: 56%

Section: Introductionmentioning

confidence: 99%

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Mechanism of the Zn(II)Phthalocyanines’ Photochemical Reactions Depending on the Number of Substituents and Geometry

et al. 2016

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Dye‐sensitized solar cells based on zinc(II) phthalocyanines bearing 3‐pyridin‐3‐ylpropoxy anchoring groups

Keleş

Bıyıklıoğlu

Güzel

et al. 2020

Applied Organom Chemis

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In this study, nonperipherally tetra-substituted (2), peripherally tetrasubstituted (3), and peripherally octa-substituted (4) zinc(II) phthalocyanines were synthesized as sensitizers for dye-sensitized solar cells (DSSCs) in which 3-pyridin-3-ylpropoxy substituent acts as anchoring unit to bind TiO 2 surface. The optical results indicated that there is an interaction between the dyes and the TiO 2 surface. The photovoltaic performances of the DSSCs based on these dyes were found to depend on both the position and number of the substituents. Despite the more red-shifted absorption, the DSSC based on 2 showed the conversion efficiency of 0.68%, which is lower than 1.36% and 0.92% for 3 and 4, respectively, under one sun (AM 1.5G). The vertical orientation of the dye on TiO 2 surface could be the main reason for the higher photovoltaic performance of complex 3, which is beneficial for not only injecting the electrons into the conduction band of TiO 2 but also reducing the charge recombination. Overall, these results demonstrate that the peripherally tetra-substituted 3-pyridin-3-ylpropoxy zinc(II) phthalocyanine complex (3) as a sensitizer can more efficiently utilize the photons in the red/near-infrared region with respect to the other complexes studied.

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A Case‐Study on the Photophysics of Chalcogen‐Substituted Zinc(II) Phthalocyanines

Ezquerra Riega,

Gutierrez Suburu,

Rodríguez

et al. 2024

Chemistry A European J

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Singlet dioxygen has been widely applied in different disciplines such as medicine (photodynamic therapy or blood sterilization), remediation (wastewater treatment) or industrial processes (fine chemicals synthesis). Particularly, it can be conveniently generated by energy transfer between a photosensitizer's triplet state and triplet dioxygen upon irradiation with visible light. Among the best photosensitizers, substituted zinc(II) phthalocyanines are prominent due to their excellent photophysical properties, which can be tuned by structural modifications, such as halogen‐ and chalcogen‐atom substitution. These patterns allow for the enhancement of spin‐orbit coupling, commonly attributed to the heavy atom effect, which correlates with the atomic number ( ) and the spin‐orbit coupling constant ( ) of the introduced heteroatom. Herein, a fully systematic analysis of the effect exerted by chalcogen atoms on the photophysical characteristics (absorption and fluorescence properties, lifetimes and singlet dioxygen photogeneration), involving 30 custom‐made β‐tetrasubstituted chalcogen‐bearing zinc(II) phthalocyanines is described and evaluated regarding the heavy atom effect. Besides, the intersystem crossing rate constants are estimated by several independent methods and a quantitative profile of the heavy atom is provided by using linear correlations between relative intersystem crossing rates and relative atomic numbers. Good linear trends for both intersystem crossing rates (S1‐T1 and T1‐S0) were obtained, with a dependency on the atomic number and the spin‐orbit coupling constant scaling as and , respectively The trend shows to be independent of the solvent and temperature.

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Modulation of the electronic and spectroscopic properties of Zn(ii) phthalocyanines by their substitution pattern

Cited by 85 publications

References 64 publications

Mechanism of the Zn(II)Phthalocyanines’ Photochemical Reactions Depending on the Number of Substituents and Geometry

Mechanism of the Zn(II)Phthalocyanines’ Photochemical Reactions Depending on the Number of Substituents and Geometry

Dye‐sensitized solar cells based on zinc(II) phthalocyanines bearing 3‐pyridin‐3‐ylpropoxy anchoring groups

A Case‐Study on the Photophysics of Chalcogen‐Substituted Zinc(II) Phthalocyanines

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