Aggregation control of robust water-soluble zinc (II) phthalocyanine-based photosensitizers
- Authors: Ikeuchi, Takuro , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Kimura, Mutsumi
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239709 , vital:50757 , xlink:href="https://doi.org/10.1021/acs.langmuir.6b03552"
- Description: A water-soluble zinc phthalocyanine (ZnPc) complex with four negatively charged electron-withdrawing sulfonic acid substituents at the nonperipheral positions (α-ZnTSPc) is found to have a high singlet oxygen (1O2) quantum yield and exhibits high photostability. The formation of aggregates is hindered and the highest occupied molecular orbital is significantly stabilized, making α-ZnTSPc potentially suitable for its use as a photosensitizer for photodynamic therapy and photoimmunotherapy. Atomic force microscopy (AFM) reveals that mixtures of the negatively charged α-ZnTSPc complex with a similar positively charged ZnPc were found to result in the self-assembly of one-dimensional accordion-like fibers. Supramolecular fibers can be formed in aqueous solutions through intermolecular electrostatic and donor–acceptor interactions between the two water-soluble ZnPcs.
- Full Text:
- Date Issued: 2016
Efficient energy transfer in ethynyl bridged corrole–BODIPY dyads
- Authors: Yan, Yu , Wu, Fan , Qin, Jiawei , Xu, Haijun , Shi, Maohu , Zhou, Jingfeng , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240899 , vital:50883 , xlink:href="https://doi.org/10.1039/C6RA12271J"
- Description: A series of new corrole–BODIPY dyads bridged by ethynyl linker moieties have been synthesized in high yields and fully characterized. The direction of energy transfer upon electronic excitation has been explored, and was found to be dependent on the number of corrole rings and their connection position on the BODIPY core. Intense bands in the absorption spectrum cover most of the visible region, which is potentially advantageous for capturing solar energy. Studies on the excitation spectra and lifetimes suggest that the energy transfer efficiency between the BODIPY and corrole moieties reaches almost 85%, which appears to be efficient in the context of energy transfer within the singlet manifold.
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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.
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- Date Issued: 2016
Optically active BODIPYs
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
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- Date Issued: 2016
Photophysical properties of tetraphenylporphyrinsubphthalocyanine conjugates
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
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- Date Issued: 2016
Spectroscopic investigations and theoretical calculations of DABCO induced xanthene bridged self-assembled zinc (II) porphyrin dimer
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
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- Date Issued: 2016
Synthesis and photophysicochemical properties of BODIPY dye functionalized gold nanorods for use in antimicrobial photodynamic therapy
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith K , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
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- Date Issued: 2016
Synthesis, characterization and electrochemistry of rhodium (iii) complexes of meso-substituted [14] tribenzotriphyrin (2.1. 1)
- Authors: Xue, Zhaoli , Wang, Yemei , Mack, John , Mkhize, Scebi , Nyokong, Tebello , Fang, Yuanyuan , Ou, Zhongping , Kadish, Karl M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241043 , vital:50899 , xlink:href="https://doi.org/10.1039/C6RA03028A"
- Description: A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a–d) with Rh2(C8H12)Cl2 provides RhIII–TriP complexes (2a–d) in 40−52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and 1H NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a–d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a–d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a–d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO–LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy π → π* transition of the [14]tribenzotriphyrin(2.1.1) π-system.
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- Date Issued: 2016
Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
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- Date Issued: 2016
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
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- Date Issued: 2015
Meso-and axially-modified IrIIItriarylcorroles with tunable electrocatalytic properties
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
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- Date Issued: 2015
Organosilicon compounds as fluorescent chemosensors for fluoride anion recognition
- Authors: Gai, Lizhi , Mack, John , Lu, Hua , Nyokong, Tebello , Li, Zhifang , Kobayashi, Nagao , Shen, Zhen
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241424 , vital:50938 , xlink:href="https://doi.org/10.1016/j.ccr.2014.10.009"
- Description: Recent developments in organosilicon-based chemosensors for F− recognition are reviewed. The design strategies for improving the photophysical properties of organosilicon-based chemosensors are elaborated, with an emphasis placed on their utility for biological applications. The photophysical properties and electronic structures are analyzed in depth with reference made to the results of molecular modeling calculation and possible future research directions are assessed.
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- Date Issued: 2015
Spectroscopic and nonlinear optical properties of the four positional isomers of 4α-(4-tert-butylphenoxy) phthalocyanine
- Authors: Ngubeni, Grace N , Britton, Jonathan , Mack, John , New, Edward , Hancox, Ian , Walker, Marc , Nyokong, Tebello , Jones, Tim S , Khene,Samson M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241448 , vital:50940 , xlink:href="https://doi.org/10.1039/C5TC01601K"
- Description: The spectroscopic and nonlinear optical properties of the positional isomers of metal free 4α-(4-tert-butylphenoxy) phthalocyanine are presented. Second order nonlinear polarizability (β), imaginary hyperpolarizability (Im(γ)) and imaginary susceptibility (Im[χ(3)]) values were determined for the four positional isomers. The measured β values of the four isomers displayed the following trend, C4h (34.0 × 10−5 m MW−1) > D2h (28.8 × 10−5 m MW−1) > C2v (22.8 × 10−5 m MW−1) > Cs (13.7 × 10−5 m MW−1).
- Full Text:
- Date Issued: 2015
Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
Synthesis, characterization and photophysical properties of an acenaphthalene fused-ring-expanded NIR absorbing aza-BODIPY dye
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189763 , vital:44929 , xlink:href="https://doi.org/10.1039/C5RA14916A"
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY.
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- Date Issued: 2015
Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith K , Mack, John , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241606 , vital:50954 , xlink:href="https://doi.org/10.1039/C4TC00505H"
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications.
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- Date Issued: 2014
Photophysicochemical properties and TD-DFT calculations of a novel terminal alkyne substituted metal free phthalocyanine
- Authors: Yilmaz, Yusuf , Mack, John , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241562 , vital:50950 , xlink:href="https://doi.org/10.1142/S1088424613501241"
- Description: The synthesis of a novel free base tetrakis(prop-2-ynyloxy)phthalocyanine (2) is described, along with its characterization by IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. The compound exhibited good solubility in a wide range of organic solvents and no significant aggregation was observed over a wide concentration range. The values for the singlet oxygen (ΦΔ), photodegradation, fluorescence (ΦF) and triplet state quantum yields and the fluorescence and triplet state lifetimes are reported. A relatively high ΦΔ value of 0.46 was obtained in DMSO. The ability to carry out "click" chemistry at the ligand periphery enhances the potential utility of 2 for use in bioconjugates in photodynamic therapy (PDT). A moderately high ΦF value of 0.18 is observed for emission in the therapeutic window in the near-IR region, which suggests that it may also be possible to determine the level of localization of 2 in tumor cells through bioimaging.
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- Date Issued: 2014
Synthesis, characterization and photodynamic therapy properties of an octa-4-tert-butylphenoxy-substituted phosphorus (V) triazatetrabenzcorrole
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
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- Date Issued: 2014
Synthesis, photophysicochemical properties and TD-DFT calculations of tetrakis (2-benzoyl-4-chlorophenoxy) phthalocyanines
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
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- Date Issued: 2014
Trends in the TD-DFT calculations of porphyrin and phthalocyanine analogs
- Authors: Mack, John , Stone, Justin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193882 , vital:45402 , xlink:href="https://doi.org/10.1142/S108842461450045X"
- Description: In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn (II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
- Full Text:
- Date Issued: 2014