Density functional study of the redox processes in subphthalocyanines

Ferro, Víctor R.; Poveda, Luis A.; Claessens, Christian G.; González-Jonte, R. H.; Vega, José Manuel García de la

doi:10.1002/qua.10408

Cited by 23 publications

(37 citation statements)

References 30 publications

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“…[28][29][30] This active space very well reproduces the electronic low-energy transitions of the SubPcs due to the breakdown of the Gouterman four level model observed in these compounds. Nevertheless, the expression for γ ijkl in a three level model is appreciably complex, and only in the case of reduced symmetry the final expression is manageable.…”

Section: Methodsmentioning

confidence: 84%

Structural Modulation of the Dipolar−Octupolar Contributions to the NLO Response in Subphthalocyanines

et al. 2005

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Second order nonlinear optical properties of a series of trinitrosubphthalocyanine (SubPc) isomers were studied experimentally by electric field induced second harmonic (EFISH) generation and hyper Rayleigh scattering (HRS). These experimental values were compared to the ones obtained theoretically employing both sum over states (SOS) and finite field (FF) methods. From these studies, it was shown that the dipolar contributions to the beta tensor are very much dependent on the substitution pattern at the periphery of the subphthalocyanine macrocycle, whereas the octupolar contributions remain mostly unchanged. Consequently, it was deduced that SubPc is extremely well suited for the decoupling of octupolar and dipolar contribution to the NLO response.

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Section: Methodsmentioning

confidence: 84%

Structural Modulation of the Dipolar−Octupolar Contributions to the NLO Response in Subphthalocyanines

et al. 2005

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“…100 µs) 57. This stabilization is likely due to the particular characteristics of the axial polar bond of SubPc, which increases its length and ionic character upon SubPc reduction,58 and the donor–acceptor topology, which may prevent an efficient orbital overlap between the reduced SubPc LUMO and the oxidized Fc HOMO.…”

Section: Electron‐donor and ‐Acceptor Properties Of Phthalocyanines Amentioning

confidence: 99%

Phthalocyanines: From outstanding electronic properties to emerging applications

Claessens

Hahn

Torres

2008

The Chemical Record

622

393

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This review paper gives a brief overview on how the outstanding chemical and physical properties of phthalocyanines and phthalocyanine derivatives are being studied and employed in order to construct state-of-the-art technological devices. In a first instance, a short account on how the nature of the phthalocyanine structure and its organization in condensed phases play an important role in their conducting and ultraviolet-visible absorption properties is presented. Consequently, these basic electronic and photophysical features of phthalocyanines allow us to explain why phthalocyanine-based multicomponent covalent or noncovalent donor-acceptor systems may give rise to very interesting photophysical properties, in particular in terms of their ability to generate very long-lived photoinduced charge-separated states. A concise survey on the organization of these multifunctional systems shows how a profound understanding of the morphology at the nanometer-scale of these phthalocyanine-based molecular materials is needed in order to control their physical properties in condensed phases. All the previously mentioned chemical and physical features combined together led us to the description of the latest attempts at incorporating phthalocyanines into photovoltaic devices for solar energy conversion and onto quantum dots for photodynamic therapy or quantum computing.

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“…This approach has been used successfully in porphyrin‐related theoretical research 21. Because the SubPcs are molecular systems that are close to porphyrins, some workers 17, 18, 20 have performed DFT calculations with success. Considering the above‐mentioned elements, in the present study, the MSubPcs were fully optimized at the B3LYP/6‐31G* level 22, 23 with C 3 v symmetry.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Recently, quantum chemical calculations 16–20 have provided realistic high‐quality descriptions of the geometrical and electronic structures of SubPcs. Gong et al 18 reported that the geometries obtained at the B3LYP level were in much better agreement with the experiment data than obtained at the Hartree–Fock (HF) level with the same basis set.…”

Section: Introductionmentioning

confidence: 99%

“…Gong et al 18 reported that the geometries obtained at the B3LYP level were in much better agreement with the experiment data than obtained at the Hartree–Fock (HF) level with the same basis set. Ferro et al 17, 20 reported the investigation of the redox processes in SubPcs and predicted a cone‐shaped structure with substitution of the center boron atom by two hydrogens, using an ab initio method. In this article, we present a theoretical study of the structure, stability, and aromaticity of MSubPc and MPc (MB, Al, and Ga).…”

Section: Introductionmentioning

confidence: 99%

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Structure, stability, and aromaticity of MSubPc (MB, Al, and Ga): Computational study

Yang

2005

Int J of Quantum Chemistry

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ABSTRACT:A theoretical investigation on the structure, stability, and aromaticity of M-subphthalocyanine (MOSubPc; MAB, Al, and Ga) was performed at the B3LYP/6-31ϩG*//B3LYP/6-31G* level. The comparison between MOSubPc and the corresponding MOphthalocyanine (MOPc) was considered. The geometry optimization of the MOSubPc shows that in the AlOSubPc and GaOSubPc, the steric repulsions among the three azacoupled isoindole moieties increase, as to their macrocycles tend to be far from planarity. The binding energies of ClOM . . . aza-coupled isoindole corrected by the basis set superposition error (BSSE), and the nucleus-independent chemical shift (NICS) values at the ring center, which are a simple and effective local aromaticity probe, were calculated. The results show that AlOSubPc is less stable than both BOSubPc and AlOPc for larger steric repulsion, smaller binding energy, and weaker aromaticity. In the same way, GaOSubPc is less stable than both BOSubPc and GaOPc. In addition, the ring expansion reactivity occurring in BOSubPc was confirmed by the global aromaticity mirrored by the electrophilicity index values. Therefore, the AlOSubPc and GaOSubPc remain unknown, while the corresponding compounds AlOPc and GaOPc are known experimentally.

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Density functional study of the redox processes in subphthalocyanines

Cited by 23 publications

References 30 publications

Structural Modulation of the Dipolar−Octupolar Contributions to the NLO Response in Subphthalocyanines

Structural Modulation of the Dipolar−Octupolar Contributions to the NLO Response in Subphthalocyanines

Phthalocyanines: From outstanding electronic properties to emerging applications

Structure, stability, and aromaticity of MSubPc (MB, Al, and Ga): Computational study

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