Comparative electronic structures and UV–vis spectra of tribenzosubporphyrin, tribenzomonoazasubporphyrin, tribenzodiazasubporphyrin, and subphthalocyanine: Insight from DFT and TDDFT calculations

Gao, Yanfang; Solntsev, Pavlo V.; Nemykin, Victor N.

doi:10.1016/j.jmgm.2012.09.003

Cited by 16 publications

(6 citation statements)

References 41 publications

(43 reference statements)

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“…23 By introducing one or two additional chlorine atoms per molecule, one would also expect the C 3v symmetry of the SubNc molecule to be broken, causing the LUMO and LUMO+1 levels to lose their degeneracy and separate. 28,32 Either of these effects could be responsible for the offset seen in the SubNc LUMO when compared with that of SubPc. Regardless of whether this is the case, it is clear that the IE and EA values we present here are for a partially chlorinated SubNc, rather than those for the pure SubNc molecule.…”

Section: Resultsmentioning

confidence: 99%

Determination of Energy Level Alignment within an Energy Cascade Organic Solar Cell

et al. 2016

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The interfacial band alignment among boron subnaphthalocyanine chloride (SubNc), boron subphthalocyanine chloride (SubPc), and α-sexithiophene (α-6T) is explored using ultraviolet, inverse, and X-ray photoemission spectroscopies (UPS, IPES, and XPS, respectively). With these tools, the ionization energy (IE) and electron affinity (EA) for each material are determined. Layer-by-layer deposition of SubPc and SubNc on α-6T as well as SubPc on SubNc, combined with UPS and IPES, allows for the direct determination of the energy level alignment at the interfaces of interest. A small dipole is found at the α-6T/SubNc/SubPc interface, expanding the donor-LUMO to acceptor-HOMO gap and explaining the large open circuit voltage obtained with these devices. However, there is a small electron barrier between SubNc and SubPc, which may limit the efficiency of electron extraction in the current device configuration. Excess chlorine may be responsible for the high IE and EA found for SubNc and could potentially be remedied with improved synthetic methods or further purification.

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Section: Resultsmentioning

confidence: 99%

Determination of Energy Level Alignment within an Energy Cascade Organic Solar Cell

et al. 2016

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“…As compared to subphthalocyanines, the Soret and Q-bands shift to the red and to the blue, respectively. Nemykin and co-workers carried out a theoretical study on these shifts based on the DFT and TDDFT calculations on a series of tribenzo-annulated molecules by changing the number of meso -nitrogen atoms from tribenzosubporphine to subphthalocyanine …”

Section: Subporphyrinsmentioning

confidence: 99%

“…Nemykin and co-workers carried out a theoretical study on these shifts based on the DFT and TDDFT calculations on a series of tribenzo-annulated molecules by changing the number of meso-nitrogen atoms from tribenzosubporphine to subphthalocyanine. 79 In the first report of the meso-aryl-substituted subporphyrins, Kobayashi et al mentioned that the types of meso-aryl groups significantly affect the relative intensities between the Q 00 band and the Q 01 vibrational band (Figure 8). 45,46 The Q 00 and Q 01 bands of 7 with 4-methoxyphenyl substituents are similarly intense, whereas the Q 00 band nearly diminishes in the case of subporphyrins with electron-withdrawing meso-aryl groups, such as 4-pyridyl (5), 3-pyridyl (6), and 4-trifluoromethylphenyl (8) groups.…”

Section: Optical and Electrochemical Properties Of Subporphyrinsmentioning

confidence: 99%

Recent Advances in Subporphyrins and Triphyrin Analogues: Contracted Porphyrins Comprising Three Pyrrole Rings

2016

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Subporphyrinato boron (subporphyrin) was elusive until the syntheses of tribenzosubporphine in 2006 and meso-aryl-substituted subporphyrin in 2007. These novel contracted analogues possess a 14π-electron conjugated system embedded in a bowl-shaped structure. They exhibit absorption and fluorescence in the UV/vis region and nonlinear optical properties due to their octupolar structures. The unique coordination geometry around the central boron atom in the structure of subporphyrin enabled investigation of rare boron species, such as borenium cations, boron hydrides, and boron peroxides. Along with the burgeoning development of the chemistry of subporphyrins, analogous triphyrin systems have also emerged. Their rich coordination chemistry as a result of their free-base structures, which are different from the boron-coordinating structure of subporphyrins, has been intensively investigated. On the basis of the unique structures and reactivities of subporphyrins and their related triphyrin analogues, supramolecular architectures and covalently linked multicomponent systems have also been actively pursued. This Review provides an overview of the development of subporphyrin and triphyrin chemistry in the past decade and future prospects in this field, which may inspire molecular design toward applications based on their unique properties.

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“…A series of different exchange-correlation functionals were corrected, including a pure generalized gradient approximation (GGA)BP86, , hybrid GGAsB3LYP and TPSSh, meta-GGAM06, and range-separated hybridsCAM-B3LYP, LC-BLYP, and ωB97X . These functionals have been widely used to carry out TD-DFT calculations of tetrapyrrolic macrocycles, − and the benefits and drawbacks of their applications have been highlighted.…”

Section: Introductionmentioning

confidence: 99%

Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV–Vis–NIR Spectra of Phthalocyanines

et al. 2019

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A methodological survey of density functional theory (DFT) methods for the prediction of UV–visible (vis)–near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm–Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV–visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAM-B3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higher-energy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2–3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV–vis–NIR spectra of phthalocyanines and related macrocycles in the years ahead.

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Comparative electronic structures and UV–vis spectra of tribenzosubporphyrin, tribenzomonoazasubporphyrin, tribenzodiazasubporphyrin, and subphthalocyanine: Insight from DFT and TDDFT calculations

Cited by 16 publications

References 41 publications

Determination of Energy Level Alignment within an Energy Cascade Organic Solar Cell

Determination of Energy Level Alignment within an Energy Cascade Organic Solar Cell

Recent Advances in Subporphyrins and Triphyrin Analogues: Contracted Porphyrins Comprising Three Pyrrole Rings

Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV–Vis–NIR Spectra of Phthalocyanines

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