UV/Vis Spectra of Subporphyrazines and Subphthalocyanines with Aluminum and Gallium: A Time‐Dependent DFT Study

Montero‐Campillo, M. Merced; Lamsabhi, Al Mokhtar; Mó, Otília; Yáñez, Manuel

doi:10.1002/cphc.201201028

Cited by 10 publications

(14 citation statements)

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“…This process is relevant since there are not many chromogenic reagents for anion detection and even fewer are effective in water or waterorganic solvent mixtures. We have found in the literature theoretical studies about the stability of different subphthalocyanines with several central atoms, 39 also studies analyzing the spectroscopic properties 40 of SubPcs but, to the best of our knowledge, there is no experimental or theoretical study analyzing the ability of subphthalocyanines to capture anions by non-covalent interactions. This may be a relevant issue, since it can produce a kind of chromogenic reagent for anion detection that can be used in water or water mixtures and that are not destroyed in the detection process, since the non-covalent interactions are weak enough to reverse the procedure.…”

Section: Introductionmentioning

confidence: 99%

Theoretical design of molecular grippers for anion recognition based on subporphyrazines and subphthalocyanines

Sánchez‐Lozano

Estévez

Hermida-Ramón

2014

Phys. Chem. Chem. Phys.

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Subphthalocyanines (SubPcs) are 14 π-electron aromatic macrocycles containing three 1,3-diiminoisoindol units N-fused around a central boron atom. Their particular concave π-extended structure makes them potentially useful in fields related to optoelectronics and molecular electronics. Also, their structure makes them potential receptors of complementary convex-shaped molecules. Inspired by the properties of subphthalocyanines and by previous studies about the possibility of obtaining neutral receptors composed of aromatic rings that can bind anions, we performed a theoretical study to analyze the ability of subphthalocyanines and some SubPc analogues to capture anions by non-covalent interactions. This may be relevant, since they can produce a variety of chromogenic reagents for anion detection that are not destroyed in the detection process, since the non-covalent interactions are weak enough to reverse the procedure. We characterized complexes formed between several SubPc derivatives and different anions, and also studied the influence of this process on the optical properties of these molecules. The stabilization trend reflected by the energetic results and the changes shown in the absorption wavelengths of the host molecule under complexation confirm our hypothesis about the possibility of these kinds of molecules being used as chromogenic reagents for anion capture, even in solvents with a large dielectric constant like water.

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Section: Introductionmentioning

confidence: 99%

Theoretical design of molecular grippers for anion recognition based on subporphyrazines and subphthalocyanines

Sánchez‐Lozano

Estévez

Hermida-Ramón

2014

Phys. Chem. Chem. Phys.

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“…More precisely, solvent shifts of the excitation bands were obtained by the nonequilibrium implementation of the PCM through single-point calculations on equilibrium geometries obtained in vacuum. This methodology has been shown to be suitable to reproduce the experimental values in systems similar to those considered in the present publication [3,6,17].…”

Section: Computational Detailsmentioning

confidence: 80%

“…The rest of the absorptions of the spectra that form the Soret or B band at lower wavelengths (around 400 nm) are associated with S0 -> S2 electronic excitations. The same model was also successfully used to rationalize the Q bands of subporphyrins [21], subporphyrazines and SubPcs [6,17,[22][23][24][25], as well as Be-SubPcs [26] complexes. As explained below, the results show that this model is also valid for the transitions observed in our set, but it needs to be expanded in some specific cases to include the HOMO-2 orbital.…”

Section: Mo Analysismentioning

confidence: 99%

“…In our group, we have previously explored, on theoretical grounds, the UV-visible spectra of SubPcs, in which the central boron atom was replaced by aluminum or gallium by using time-dependent DFT calculations, including chloroform as a solvent [17]. This replacement led to a redshift of the Q band, which is not very dependent on either the nature of the peripheral substituents or the nature of the central atom.…”

Section: Introductionmentioning

confidence: 99%

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A Theoretical Survey of the UV–Visible Spectra of Axially and Peripherally Substituted Boron Subphthalocyanines

et al. 2022

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The UV–visible spectra of a series of subphthalocyanines (SubPcs) characterized by three different axial substituents (An) in combination with H, F, NO2, SO2H and SO2CH3 peripheral substituents (Ri) were predicted and analyzed by means of time-dependent DFT calculations, including chloroform as a solvent. In this analysis, we paid particular attention to the Q band, which remained almost unchanged regardless of the nature of the axial substituent. For the same axial substituent, changes in the Q band were also rather small when hydrogens at the periphery were replaced by R1 = SO2H and R1 = R2 = SO2H. However, the shifting of the Q band was almost 10 times larger when R1 = NO2 and R1 = R2 = NO2 due to the participation of this substituent in the π SubPc cloud. In most cases, the characteristics of the spectra can be explained considering only the transitions involving the HOMO-1, HOMO, LUMO and LUMO + 1 orbitals, where the Q band can be decomposed into two main contributions, leading to charge separation. Only for SubPc(A3,F,F,H) would one of the two contributions from the deepest orbital involved not lead to charge transfer. For this latter case, the HOMO-2 orbital must also be taken into account. In summary, the results obtained with the analysis of the MO indicate that the studied SubPcs are appropriate for photochemical devices.

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“…[8][9][10][11] These SubPc compounds (see Figure 1) are non-planar contracted porphyrinoids containing a 14 π electron aromatic core and present a very promising photochemical behavior. 12 As shown by previous experimental and theoretical studies, [13][14][15] photochemical properties of SubPc compounds depend strongly on the peripheral and axial substituents, as well as on the nature of the cation that occupies the central cavity. In this field the synergy theory-experiment has been shown to be particularly useful, since ab initio or Density Functional Theory (DFT) calculations may provide useful a priori information on the expected behavior of particular derivatives prior to any synthesis attempt.…”

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confidence: 99%

Beryllium subphthalocyanines self-assembling properties

2016

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INTRODUCTIONFundamental biological functions such as photosynthesis or cellular respiration are carried out by porphyrins, a huge, relevant family of macrocycles in organic synthesis. 1-2 From a structural point of view, porphyrines are highly conjugated systems that generate nowadays as much interest as in the early years, in particular in material science and medicine. [3][4][5][6][7] Many analogues of porphyrins have been obtained in the last years in the search for new materials, as for instance subphthalocyanines (SubPc) or subporphyrazines (SubPz). [8][9][10][11] These SubPc compounds (see Figure 1) are non-planar contracted porphyrinoids containing a 14 π electron aromatic core and present a very promising photochemical behavior. 12 As shown by previous experimental and theoretical studies, [13][14][15] photochemical properties of SubPc compounds depend strongly on the peripheral and axial substituents, as well as on the nature of the cation that occupies the central cavity. In this field the synergy theory-experiment has been shown to be particularly useful, since ab initio or Density Functional Theory (DFT) calculations may provide useful a priori information on the expected behavior of particular derivatives prior to any synthesis attempt. This approach permits to save much time and efforts in the preparation of compounds for which it is possible to predict, on theoretical grounds, whether they are going to have low or null photochemical activity, or on the contrary to focus the efforts in the synthesis of those systems for which a high photochemical activity is predicted. [16][17][18][19][20][21] In this direction, very recently, beryllium subphthalocyanines were shown to be able of absorbing light in the visible region. 22 This fact is a new evidence of the chemical versatility of beryllium, whose ability to behave as an effective Lewis acid, by forming beryllium bonds, opens a door to modulate or completely modify the intrinsic physicochemical properties of its conjugated Lewis base. 23-25When the final goal is to design compounds with a high potential photochemical activity, it is not enough to verify that indeed this is the case for isolated systems. The preparation of the devices to be used in practical applications requires the active compounds to be able to form large enough molecular assemblies, which can work as a molecular wire. This is actually the main objective of this paper, to investigate the selfassembling capacity of Be derivatives which have been recently found to be good components of photovoltaic devices, in view of the photochemical activity of the isolated systems. BePc when crystallizing. This is not only due to the different size and shape of the macrocycles or differences between Be and B atoms, but also to the R substituents which largely affect the packing along the three dimensions and determine the supramolecular oganization. 31 In the BSubPc crystal, parallel columns of aggregates are distorted along the c axis, avoiding the alignment of the B-F bonds. Additiona...

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UV/Vis Spectra of Subporphyrazines and Subphthalocyanines with Aluminum and Gallium: A Time‐Dependent DFT Study

Cited by 10 publications

References 58 publications

Theoretical design of molecular grippers for anion recognition based on subporphyrazines and subphthalocyanines

Theoretical design of molecular grippers for anion recognition based on subporphyrazines and subphthalocyanines

A Theoretical Survey of the UV–Visible Spectra of Axially and Peripherally Substituted Boron Subphthalocyanines

Beryllium subphthalocyanines self-assembling properties

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