A theoretical study of subphthalocyanine and its nitro- and tertbutyl-derivatives

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

doi:10.1016/s0166-1280(00)00679-5

Cited by 32 publications

(53 citation statements)

References 31 publications

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“…Furthermore, we have considered the influence of intermolecular interactions on the geometry and electronic parameters for describing SubPcs. These interactions may play a significant role in the first steps of the ring expansion reaction and they may also help us to understand the differences observed between the solid state geometries and the ones calculated in the gas phase [17,18]. In our previous calculations the biggest relative deviation of the calculated geometrical parameters with respect to the experimental ones in the solid state correspond, as a rule, to the B-Cl bond.…”

Section: Models and Computational Detailsmentioning

confidence: 71%

“…Furthermore, Engel et al [19] have concluded that the solid state arrangement of SubPc complexes is mostly determined by the nature and size of the axial ligand. Additionally, we have shown [18] that the B-Cl distance systematically varies with the electron donor/acceptor nature of the peripheral substituents. The electron-donor substitution (tertbutyl-SubPc) gives rise to the lengthening of this distance while the electron-withdrawing substitution (nitro-SubPc) gives the opposite effect.…”

Section: Introductionmentioning

confidence: 90%

“…Nonetheless, few papers have been published with respect to this topic [15][16][17][18]. They are, of course, insufficient for fully explaining most of the chemical and physical properties of these compounds.…”

Section: Introductionmentioning

confidence: 99%

“…They are, of course, insufficient for fully explaining most of the chemical and physical properties of these compounds. Recently, we achieved a theoretical investigation of the molecular electronic structure of SubPc and some of its peripheral substituted derivatives at semiempirical and ab initio levels [17,18].…”

Section: Introductionmentioning

confidence: 99%

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The axial coordination in subphthalocyanines: Geometrical and electronic aspects

Ferro

Vega

Claessens

et al. 2001

J. Porphyrins Phthalocyanines

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Theoretical calculations were performed for studying the electronic molecular structure of axial subphthalocyanine (SubPc) derivatives. The intermolecular SubPc interactions were also investigated at theoretical level using adequate models. These models represent the interaction of one Cl(OR)-SubPc with the surrounding molecules through the Cl atom as well as the interaction of the Cl-SubPc with an incoming diiminoisoindole group in the first steps of the open ring reaction. The SubPc complexes with more electronegative atoms than Cl heteroatoms in apical positions are more pyramidal than Cl-SubPc. The B-X and B-Np are the most sensitive macrocycle positions with respect to the axial substitutions in SubPcs. The B-X bond has an elevated polarity and seems to correlate with the chemical reactivity of these compounds. The theoretical calculations of the near-frontier orbitals reveal an outstanding energetic and structural homogeneity along the studied series which is in correspondence with the fact that the axial ligand has only a small influence on the position of the maximum bands in UV-vis spectra as well as in the first half-wave potentials for oxidative processes. The study of the intermolecular interactions give information about their influence on the molecular structure of the axial complexes of the SubPcs. The characterization of the interaction of one Cl-SubPc with a pyrrol containing group may be useful in the understanding of the mechanism of the ring expansion reactions. In general, the present results indicate that the apical position may be a critical reactive center both for redox and axial substitution processes.

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Section: Models and Computational Detailsmentioning

confidence: 71%

Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The axial coordination in subphthalocyanines: Geometrical and electronic aspects

Ferro

Vega

Claessens

et al. 2001

J. Porphyrins Phthalocyanines

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“…This result is not strange, because it is well-known that the calculated band gap in many cases does not agree with the experimental value. 38,39 …”

Section: Electrochemical Characterizationmentioning

confidence: 99%

Electrochemical and Computational Study of Copper (Ii) Alkylpyrazolone Based Enamine Complex

Moreno¹,

Belmar²,

Brovelli³

et al. 2008

J. Chil. Chem. Soc.

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The cyclic voltammograms (CV) of the copper complex CuL 2 , L: C 19 H 26 N 3 O [1-(n-hexyl)-3-methyl-4-[1-phenylaminopropylidene]-2-pyrazolin-5-one] have been studied. The CV profiles of CuL 2 show one or two reduction and oxidation wave. The energy level corresponding to the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of CuL 2 have been determined experimentally from the first oxidation and reduction onset potential, respectively. These values were also estimated from Density Functional calculations. The electrochemical energy gap deduced from these measurements (E g ~ 1.03 eV) agrees quite well with the theoretical value.

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The σ‐donating and π‐accepting properties of ortho‐Si(CH₃)₃ phosphinine macrocycles

Ferro

Omar

González-Jonte

et al. 2003

Heteroatom Chemistry

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A theoretical study of subphthalocyanine and its nitro- and tertbutyl-derivatives

Cited by 32 publications

References 31 publications

The axial coordination in subphthalocyanines: Geometrical and electronic aspects

The axial coordination in subphthalocyanines: Geometrical and electronic aspects

Electrochemical and Computational Study of Copper (Ii) Alkylpyrazolone Based Enamine Complex

The σ‐donating and π‐accepting properties of ortho‐Si(CH₃)₃ phosphinine macrocycles

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A theoretical study of subphthalocyanine and its nitro- and tertbutyl-derivatives

Cited by 32 publications

References 31 publications

The axial coordination in subphthalocyanines: Geometrical and electronic aspects

The axial coordination in subphthalocyanines: Geometrical and electronic aspects

Electrochemical and Computational Study of Copper (Ii) Alkylpyrazolone Based Enamine Complex

The σ‐donating and π‐accepting properties of ortho‐Si(CH3)3 phosphinine macrocycles

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The σ‐donating and π‐accepting properties of ortho‐Si(CH₃)₃ phosphinine macrocycles