Preparation of phthalocyanines fused with four tetrathiafulvalene units via the functional group transformation of tetrakis(o-xylylenedithio)phthalocyanines with toluene/aluminum chloride

2014 ◽  
Vol 18 (10n11) ◽  
pp. 884-890 ◽  
Author(s):  
Takeshi Kimura ◽  
Tadafumi Chiba ◽  
Shiduko Nakajo
Keyword(s):  
Cyclic Voltammetry ◽  
Optical Properties ◽  
Aluminum Chloride ◽  
Nickel Complex ◽  
Functional Group ◽  
H Nmr ◽  
Vis Spectroscopy ◽  
Thiolate Anions ◽  
Functional Group Transformation ◽  
Tof Ms

Tetrakis(o-xylylenedithio)phthalocyanine 5 and its nickel complex 5-Ni were treated with aluminum chloride in toluene to eliminate the peripheral o-xylylene groups. The thiolate anions generated from 5 and 5-Ni were reacted with carbonyldiimidazole to produce phthalocyanines 6 and 6-Ni with four 1,3-dithiole-2-one rings, respectively. Phthalocyanine 7a having four ethylenedithiotetrathiafulvalene units was prepared via the condensation of 6-Ni with ethylenedithio-1,3-dithiole-2-thiones. The reaction of 6-Ni with bis(methylthio)-1,3-dithiole-2-thiones gave phthalocyanine 7b with the corresponding TTF units. The structures of the products were determined by 1 H NMR and MALDI-TOF-MS. Their electrochemical and optical properties were examined by cyclic voltammetry and UV-vis spectroscopy.

Preparation and electrochemical and optical properties of α-octaalkylphthalocyanines with four fused TTF units

2011 ◽  
Vol 15 (07n08) ◽  
pp. 547-554 ◽  
Author(s):  
Takeshi Kimura ◽  
Toshiharu Namauo ◽  
Kaori Amano ◽  
Nobuhiro Takahashi ◽  
Yutaka Takaguchi ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Optical Properties ◽  
Absorption Spectrum ◽  
Molecular Orbital ◽  
Molecular Orbital Calculations ◽  
Maldi Tof Ms ◽  
H Nmr ◽  
Maldi Tof ◽  
Tof Ms

3,6-Dialkylphthalonitriles (6a) and (6b) with a fused TTF unit at 4,5-positions were prepared from dialkyltetrabromobenzenes via five step reactions (alkyl: butyl and octyl). Compounds 6a and 6b were treated with lithium in n-hexanol at 120 °C for 3 h to produce α-octaalkyltetrakis(tetrathiafulvaleno)phthalocyanines (8a) and (8b), respectively. The structure of the products was determined by 1H NMR, FAB MS, and MALDI TOF MS. The 1H NMR measurement was performed in chloroform-d at around 55 °C because of their higher aggregative property. Electrochemical and optical properties of 8a and 8b were examined by cyclic voltammetry and UV-vis and MCD spectroscopy. Molecular orbital calculations succeeded in reproducing the observed absorption spectrum of tetrakis(tetrathiafulvaleno)phthalocyanine.

Synthesis of perialkynylated tetrapyrazinoporphyrazines and its Optical Properties

2009 ◽  
Vol 2009 (5) ◽  
pp. 312-316 ◽  
Author(s):  
Chun Keun Jang ◽  
Jae Yun Jaung
Keyword(s):  
Optical Properties ◽  
Nmr Spectroscopy ◽  
Laser Desorption ◽  
Diels Alder ◽  
Visible Spectroscopy ◽  
H Nmr ◽  
Uv Visible ◽  
Tof Ms ◽  
Matrix Assisted Laser ◽  
Matrix Assisted Laser Desorption

Some phthalocyanines soluble in organic solvents have been developed by peripheral introduction of substituent groups. We report a new method for preparation of the polyphenyl-substituted dicyanopyrazines based on the [2 + 4] Diels-Alder cycloaddition of the tetraphenylcyclopentadienone to an ethynyl compound. The synthesised tetrapyrazinoporphyrazinato metal complexes were characterised by UV-visible spectroscopy, MALDI-TOF-Ms (matrix-assisted laser desorption ionisation time-of-flight mass) spectroscopy, and 1H NMR spectroscopy.

(Aminophenyl)porphyrins as precursors for the synthesis of porphyrin-modified siloxanes

2019 ◽  
Vol 23 (09) ◽  
pp. 1001-1012
Author(s):  
José Almeida ◽  
Maria E. Fortună ◽  
Lucia Pricop ◽  
Andrei Lobiuc ◽  
Andreia Leite ◽  
...  
Keyword(s):  
Optical Properties ◽  
Microwave Irradiation ◽  
Functional Groups ◽  
Emission Spectra ◽  
Efficient Synthesis ◽  
Subsequent Reaction ◽  
Maldi Tof Ms ◽  
Absorption And Emission ◽  
H Nmr ◽  
Tof Ms

The present research reports the efficient synthesis of mono- and di-(aminophenyl)porphyrins and their metalation with Zn(II) using microwave irradiation. The subsequent reaction of amino-functionalized porphyrins with siloxane moieties bearing epoxy or carboxyl functional groups provided four new porphyrin-modified siloxanes. The structure of the resulting derivatives was established by 1H-NMR and MALDI-TOF-MS. The optical properties of the porphyrin chromophores were preserved, as proven by comparing the absorption and emission spectra of the initial porphyrins to those of the porphyrin-modified siloxanes.

scholarly journals Synthesis and Study of Chemical, Thermal, Mesomorphic, and Optical Properties of Terphenyls Modified with Nitrile Groups

2017 ◽  
Vol 2017 ◽  
pp. 1-9 ◽  
Author(s):  
M. L. Mota González ◽  
A. Carrillo Castillo ◽  
R. C. Ambrosio Lázaro ◽  
J. Flores Méndez ◽  
Mario Moreno ◽  
...  
Keyword(s):  
Optical Properties ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Photoluminescence Properties ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
H Nmr ◽  
Cross Coupling Reaction ◽  
Vis Spectroscopy

We report the synthesis, characterization, and the thermotropic and photoluminescence properties of dialkoxyterphenyls with (T12-CN and T12-2CN) and without (T12) nitrile groups. These terphenyls were prepared through the Suzuki-Miyaura cross-coupling reaction using a palladium-based catalyst. The products obtained were analyzed as powders or after being drop-casted or spin-coated on glass. Nuclear Magnetic Resonance (1H NMR) and Fourier Transform Infrared (FTIR) spectroscopy techniques confirmed the structure and purity of the synthesized terphenyls. The mesomorphic behavior was studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD). T12 developed various mesophases, whereas T12-CN and T12-2CN displayed one single mesophase of low order over a wide temperature range. The films topology was studied by AFM and the optical properties were determined by ultraviolet-visible (UV-Vis) spectroscopy and spectrofluorometry. Higher roughness was found for the films prepared with the asymmetric terphenyl (T12-CN). The photoluminescence (PL) spectrum obtained for the asymmetric terphenyl (T12-CN) exhibited the expected characteristics with an emission band centered at 381 nm and an overtone around 760 nm.

Structural and electrochemical comparison of trinuclear ruthenium oxo clusters [Ru3(OAc)6O(L)3]+and [Ru3(OAc)6O(L)2(CO)] (L = imidazole, benzimidazole, and 4-phenylpyridine)

2018 ◽  
Vol 74 (11) ◽  
pp. 1487-1494 ◽  
Author(s):  
Brandon Derstine ◽  
Carmen Chamberlain ◽  
Morgan Glover ◽  
Lindsey Porter ◽  
Amanda Eckermann
Keyword(s):  
Cyclic Voltammetry ◽  
Optical Properties ◽  
Single Crystal ◽  
Structure Analysis ◽  
Mixed Valence ◽  
Neutral State ◽  
X Ray ◽  
Redox Couples ◽  
Reversible Redox ◽  
Vis Spectroscopy

The triruthenium oxo clusters [Ru3(OAc)6O(L)3]+ and [Ru3(OAc)6O(L)2(CO)] possess unique electronic characteristics that vary based on the ligands L. Here we report an investigation of the structural, electrochemical, and optical properties of clusters with imidazole, benzimidazole, and 4-phenylpyridine ligands. The complexes [Ru3(OAc)6O(L)3]+ [1+ : L = imidazole (im); 2+ : L = benzimidazole (benzim); 3+ : L = 4-phenylpyridine (4PP)] and [Ru3(OAc)6O(L)2(CO)] (1-CO and 3-CO) were synthesized by reaction of either [Ru3(OAc)6O(MeOH)3]+ or [Ru3(OAc)6O(MeOH)2(CO)], respectively, with the corresponding heterocycle. We further discovered that [3]OAc could be reduced to the mixed-valence neutral state 3 by refluxing the complex under nitrogen in methanol. Single-crystal X-ray structure analysis of hexa-μ2-acetato-μ3-oxido-tris(1H-imidazole)triruthenium hexafluorophosphate acetonitrile hemisolvate, [Ru3(C2H3O2)6O(C3H4N2)3]PF6·0.5CH3CN, [1]PF6 , hexa-μ2-acetato-carbonylbis(1H-imidazole)-μ3-oxido-triruthenium methanol monosolvate, [Ru3(C2H3O2)6O(C3H4N2)(CO)]·CH3OH, 1-CO, hexa-μ2-acetato-μ3-oxido-tris(4-phenylpyridine)triruthenium pentahydrate, [Ru3(C2H3O2)6O(C11H9N)3]·5H2O, 3, and hexa-μ2-acetato-carbonyl-μ3-oxido-bis(4-phenylpyridine)triruthenium methanol monosolvate, [Ru3(C2H3O2)6O(C11H9N)2(CO)]·CH3OH, 3-CO, show the expected triruthenium μ3-oxo core and N-coordination of the ligands. Cyclic voltammetry revealed quasi-reversible and irreversible redox couples in [1]PF6 , 1-CO, and [2]PF6 , while [3]PF6 and 3-CO exhibit reversible redox couples. The optical properties of these richly colored species were investigated using UV–Vis spectroscopy.

Synthesis and optical properties of tetrapyrazino-porphyrazines containing camphorquinone group

2009 ◽  
Vol 13 (07) ◽  
pp. 794-797 ◽  
Author(s):  
Chun Keun Jang ◽  
Seung Hwan Byun ◽  
Song Hak Kim ◽  
Do Kyung Lee ◽  
Jae Yun Jaung
Keyword(s):  
Optical Properties ◽  
Nmr Spectroscopy ◽  
Fluorescence Spectroscopy ◽  
Elemental Analysis ◽  
Infrared Radiation ◽  
Condensation Reaction ◽  
Visible Spectroscopy ◽  
H Nmr ◽  
Uv Visible ◽  
Tof Ms

2,3-dicyanopyrazine and metallophthalocyanines were synthesized with magnesium containing (±)camphorquinone substituent. 2,3-dicyanopyrazine was prepared by condensation reaction of diaminomaleonitrile (DAMN) with 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione (1). The tetrapyrazinoporphyrazine was characterized by a combination of UV-visible spectroscopy, fluorescence spectroscopy, infrared radiation, elemental analysis, MALDI-TOF-MS and 1H NMR spectroscopy.

Cyclic butadiyne-linked porphyrin(2.1.2.1) oligomers

2020 ◽  
Vol 24 (01n03) ◽  
pp. 489-497 ◽  
Author(s):  
Daiki Kuzuhara ◽  
Wataru Furukawa ◽  
Naoki Aratani ◽  
Hiroko Yamada
Keyword(s):  
Cyclic Voltammetry ◽  
Nmr Spectroscopy ◽  
Fluorescence Spectra ◽  
Theoretical Calculations ◽  
Cyclic Structure ◽  
Absorption And Fluorescence Spectra ◽  
H Nmr ◽  
Reduction Potentials ◽  
Cyclic Trimer ◽  
Tof Ms

Cyclic butadiyne-linked porphyrin(2.1.2.1) oligomers are synthesized from 5,16-diethynylporphyrin(2.1.2.1) by Glaser–Hay coupling. Porphyrin(2.1.2.1) forms a bent structure which gives advantages for making cyclic structure without templating molecules. We isolated cyclic trimer and tetramer and characterized them by MALDI-TOF-MS and [Formula: see text]H NMR spectroscopy, theoretical calculations, UV-vis absorption and fluorescence spectra and cyclic voltammetry. The cyclic structure mainly affects the reduction potentials because of expansion of [Formula: see text]-conjugations through butadiyne-linkages to stabilize their LUMOs.

Modification of optical properties of PC-PBT/Cr2O3 and PC-PBT/CdS nanocomposites by gamma irradiation

2020 ◽  
Vol 92 (2) ◽  
pp. 20402
Author(s):  
Kaoutar Benthami ◽  
Mai ME. Barakat ◽  
Samir A. Nouh
Keyword(s):  
Refractive Index ◽  
Optical Properties ◽  
Band Gap ◽  
Color Difference ◽  
Band Gap Energy ◽  
Polybutylene Terephthalate ◽  
Γ Irradiation ◽  
Gap Energy ◽  
Vis Spectroscopy ◽  
Oxygen Atoms

Nanocomposite (NCP) films of polycarbonate-polybutylene terephthalate (PC-PBT) blend as a host material to Cr2O3 and CdS nanoparticles (NPs) were fabricated by both thermolysis and casting techniques. Samples from the PC-PBT/Cr2O3 and PC-PBT/CdS NCPs were irradiated using different doses (20–110 kGy) of γ radiation. The induced modifications in the optical properties of the γ irradiated NCPs have been studied as a function of γ dose using UV Vis spectroscopy and CIE color difference method. Optical dielectric loss and Tauc's model were used to estimate the optical band gaps of the NCP films and to identify the types of electronic transition. The value of optical band gap energy of PC-PBT/Cr2O3 NCP was reduced from 3.23 to 3.06 upon γ irradiation up to 110 kGy, while it decreased from 4.26 to 4.14 eV for PC-PBT/CdS NCP, indicating the growth of disordered phase in both NCPs. This was accompanied by a rise in the refractive index for both the PC-PBT/Cr2O3 and PC-PBT/CdS NCP films, leading to an enhancement in their isotropic nature. The Cr2O3 NPs were found to be more effective in changing the band gap energy and refractive index due to the presence of excess oxygen atoms that help with the oxygen atoms of the carbonyl group in increasing the chance of covalent bonds formation between the NPs and the PC-PBT blend. Moreover, the color intensity, ΔE has been computed; results show that both the two synthesized NCPs have a response to color alteration by γ irradiation, but the PC-PBT/Cr2O3 has a more response since the values of ΔE achieved a significant color difference >5 which is an acceptable match in commercial reproduction on printing presses. According to the resulting enhancement in the optical characteristics of the developed NCPs, they can be a suitable candidate as activate materials in optoelectronic devices, or shielding sheets for solar cells.

scholarly journals Synthesis of PVA/CeO2 Based Nanocomposites with Tuned Refractive Index and Reduced Absorption Edge: Structural and Optical Studies

Materials ◽  
2021 ◽  
Vol 14 (6) ◽  
pp. 1570
Author(s):  
Shujahadeen B. Aziz ◽  
Elham M. A. Dannoun ◽  
Dana A. Tahir ◽  
Sarkawt A. Hussen ◽  
Rebar T. Abdulwahid ◽  
...  
Keyword(s):  
Refractive Index ◽  
Optical Properties ◽  
Absorption Edge ◽  
Ceo2 Nanoparticles ◽  
Poly Vinyl Alcohol ◽  
Optical Parameters ◽  
Single Oscillator Model ◽  
Vis Spectroscopy ◽  
The Impact ◽  
Host Polymer

In the current study, polymer nanocomposites (NCPs) based on poly (vinyl alcohol) (PVA) with altered refractive index and absorption edge were synthesized by means of a solution cast technique. The characterization techniques of UV–Vis spectroscopy and XRD were used to inspect the structural and optical properties of the prepared films. The XRD patterns of the doped samples have shown clear amendments in the structural properties of the PVA host polymer. Various optical parameters were studied to get more insights about the influence of CeO2 on optical properties of PVA. On the insertion of CeO2 nanoparticles (NPs) into the PVA matrix, the absorption edge was found to move to reduced photon energy sides. It was concluded that the CeO2 nanoparticles can be used to tune the refractive index (n) of the host polymer, and it reached up to 1.93 for 7 wt.% of CeO2 content. A detailed study of the bandgap (BG) was conducted using two approaches. The outcomes have confirmed the impact of the nanofiller on the BG reduction of the host polymer. The results of the optical BG study highlighted that it is crucial to address the ɛ” parameter during the BG analysis, and it is considered as a useful tool to specify the type of electronic transitions. Finally, the dispersion region of n is conferred in terms of the Wemple–DiDomenico single oscillator model.

scholarly journals UV-A Treatment of ZrO2 Thin Films Fabricated by Environmental Friendlier Water-Based Solution Processing: Structural and Optical Studies

Coatings ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 821
Author(s):  
Aneeqa Bashir ◽  
Mehwish Farooq ◽  
Abdul Malik ◽  
Shahzad Naseem ◽  
Arshad Saleem Bhatti
Keyword(s):  
Optical Properties ◽  
Low Cost ◽  
Annealed Film ◽  
Optical Transmittance ◽  
Amorphous Structure ◽  
Solution Processing ◽  
Vis Spectroscopy ◽  
Water Based ◽  
Free Films ◽  
Quartz Substrates

An environmentally friendlier solution processing has been introduced to fabricate zirconium oxide (ZrO2) films on quartz substrates, using spin coating of simple water-based solution. The films cured with UV-A = 330 nm for different times (40, 80, 120 min) were investigated for structural and optical properties and compared with thermally annealed film (at 350 °C). XRD and Raman spectroscopy showed amorphous structure in all the samples with no significant phase transformation with UV-A exposure. AFM microscopy showed smooth and crack free films with surface roughness ≤2 nm that reduced with UV-A exposure. Ultraviolet-visible (UV–Vis) spectroscopy demonstrated optical transmittance ≥88% and energy band gap variations as 4.52–4.70 eV. Optical constants were found from spectroscopic ellipsometry (SE). The refractive index (n) values, measured at 470 nm increased from 1.73 to 2.74 as the UV-A exposure prolonged indicating densification and decreasing porosity of the films. The extinction coefficient k decreased from 0.32 to 0.19 indicating reduced optical losses in the films under the UV-A exposure. The photoluminescence (PL) spectra exhibited more pronounced UV emissions which grew intense with UV-A exposure thereby improving the film quality. It is concluded that UV-A irradiation can significantly enhance the optical properties of ZrO2 films with minimal changes induced in the structure as compared to thermally treated film. Moreover, the present work indicates that water-based solution processing has the potential to produce high-quality ZrO2 films for low cost and environmental friendlier technologies. The work also highlights the use of UV-A radiations as an alternate to high temperature thermal annealing for improved quality.

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