Low-Symmetry Phthalocyanines Bearing Carboxy-Groups
- Authors: Bunin, Dmitry A , Ndebele, Nobuhle , Martynov, Alexander G , Mack, John , Gorbunova, Yulia G , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231262 , vital:49870 , xlink:href="https://doi.org/10.3390/molecules27020524" "
- Description: The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.
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- Date Issued: 2022
Optical limiting properties, structure and simplified TD-DFT calculations of scandium tetra-15-crown-5 phthalocyaninates:
- Authors: May, Aviwe K , Majumdar, Poulomi , Martynov, Alexander G , Lapkina, Lyudmila A , Troyanov, Sergey I , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/163553 , vital:41048 , https://0-doi.org.wam.seals.ac.za/10.1142/S108842462050011X
- Description: The optical limiting properties of crown-ether-substituted scandium(III) phthalocyaninate complexes, bis-tetra-15-crown-5-phthalocyaninates Sc[(15C5)4Pc]∙022•0 (I) and Sc[(15C5)4Pc]−22− (Ia), together with monophthalocyaninate [(15C5)4Pc]Sc(OAc) (II) were measured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns).
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- Date Issued: 2020
Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: 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 CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy 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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- Date Issued: 2019
Photophysics and NLO properties of Ga (III) and In (III) phthalocyaninates bearing diethyleneglycol chains
- Authors: Managa, Muthumuni , Khene, Samson M , Britton, Jonathan , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Y , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/237822 , vital:50556 , xlink:href="https://doi.org/10.1142/S1088424618500128"
- Description: This work reports on synthesis and characterizations of Ga(III) and In(III) complexes, formed by 2,3-bis[2′′-(2′′′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxy phthalocyanine (1H2) coordinating acetatoindium(III) (1InOAc) and hydroxogallium(III) (1GaOH) Photophysical properties of hydroxogallium(III) phthalocyaninate 1GaOH and acetatoindium(III) phthalocyaninate 1InOAc were studied by UV-vis, fluorescence spectroscopy and time-resolved methods. The nonlinear absorption of the complexes was studied using the Z-scan technique at 532 nm and 10 ns pulse in DMSO and in thin films formed by composite with poly(bisphenol A carbonate) — PBC. The magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work showed that complex 1InOAc exhibited the strongest nonlinear optical behavior in comparison with 1GaOH in solution and a reverse tendency when embedded in PBC thin films. DFT calculations were used to rationalize these results.
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- Date Issued: 2018
Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
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- Date Issued: 2017
First example of nonlinear optical materials based on nanoconjugates of sandwich phthalocyanines with quantum dots
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
Optical limiters with improved performance based on nanoconjugates of thiol substituted phthalocyanine with CdSe quantum dots and Ag nanoparticles
- Authors: Oluwole, David O , Yagodin, Alexey V , Britton, Jonathan , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238286 , vital:50605 , xlink:href="https://doi.org/10.1039/C7DT03867D"
- Description: Two alternative synthetic approaches affording a low-symmetry A3B-type phthalocyanine 1 bearing two [2′-(2′′-mercaptoethoxy)ethoxy] anchoring substituents were developed. Due to the presence of thiol groups, this phthalocyanine could be conjugated with TOPO-capped (TOPO - trioctylphosphine)-capped CdSe quantum dots (CdSe-QDs) or oleylamine capped silver nanoparticles (Ag-NPs). The nonlinear optical behaviour of starting phthalocyanine, quantum dots, nanoparticles and their conjugates was studied by using an open aperture Z-scan technique, revealing that the grafting of 1 onto the nanomaterials resulted in a significant enhancement of the optical limiting of 1-Ag and 1-CdSe in comparison with the individual components. The conjugate 1-CdSe, being the first example of Pc-based thiol conjugated with quantum dots, revealed superior limiting characteristics with a limiting threshold below 0.18 J cm−2.
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- Date Issued: 2017
Improvement of nonlinear optical properties of phthalocyanine bearing diethyleneglycole chains
- Authors: Britton, Jonathan , Martynov, Alexander G , Oluwole, David O , Gorbunova, Yulia G , Tsivadze, Yulia G , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239812 , vital:50769 , xlink:href="https://doi.org/10.1142/S1088424616501042"
- Description: This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxyphthalocyanine 1H22 and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H22 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)χ(3)]/αα, βeffβeff, and γγ for 1H22in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)χ(3)]/αα values of the order of 10−11−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H22 were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[χ(3)χ(3)]/αα was almost three times higher in comparison with 1H22 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation
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- Date Issued: 2016
MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016