Metallo complexes of meso-phenothiazinylporphyrins: Synthesis, linear and nonlinear optical properties

Brém, Balazs; Gál, Emese; Găină, Luiza; Cristea, Castelia; Gabudean, Ana-Maria; Aştilean, Simion; Silaghi‐Dumitrescu, Luminiţa

doi:10.1016/j.dyepig.2015.08.021

Cited by 16 publications

(10 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Section: Characterizationmentioning

confidence: 99%

“…After formation of complexes (4b-d), the signal peak at −2.73 ppm disappeared, since the hydrogen atom in the N−H bond is replaced by a metal ion. 33 In some paramagnetic metalloporphyrins the signals may be broad due to the hyperfine electron-nuclear interactions and by relaxation processes.11 Figure 1 shows that compounds 4c (cobalt porphyrin) and 4d (copper porphyrin) presented this phenomenon, thus indicating the paramagnetic character of these metals.13 C NMR data to 4a showed signals that confirm the presence of alkyl (13.85-35.83 ppm), ethers (66.22 ppm) and aromatic groups (111.37-158.45 ppm). Similar signals were observed for metalloporphyrins 4b-d ( Figure S1).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Characterization and Dielectric Properties of New 5-(4-Hydroxyphenyl)-10,15,20-tri-4-[2-(3-pentadecylphenoxy)ethoxy]phenyl porphyrin and Their Ni, Co and Cu Complexes

Mota¹,

Júnior²,

Ribeiro³

et al. 2016

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

New asymmetric cardanol-based porphyrins, free-base and coordinated with Ni, Co and Cu, were synthesized and completely characterized as A3B type. Such porphyrins were obtained aiming improved solubility in polar solvents due insertion of an −OH phenolic group. Their thermal and dielectric properties were also evaluated. Changes in the synthetic route reduced the reaction time and improved the yields of the aldehyde precursor obtainment. Electronic absorption spectra of the new porphyrins in CH 2 Cl 2 , EtOH and acetone, indicated a decrease in the ε (molar absorptivity) values with increasing solvent polarity, except for the nickel complex which, in acetone, showed a slight increase of 2% in the ε value. The dielectric measurements showed that the conductivity (σ) and the loss tangent (tan δ) increased with frequency, but the permittivity (ε') decreased. The results showed that the coordination of the porphyrin promoted a significant change in thermal and dielectric properties, specially for to the Ni-complex compound, which presented the best dielectric properties with interesting values of permittivity and loss tangent at 100 MHz (19.46 and 0.011 a.u., respectively). Keywords: asymmetric porphyrins, cardanol, dielectric properties IntroductionPorphyrins are relatively planar aromatic system consisting of four pyrrole type rings joined by four methynic carbons. They have attracted scientists from many areas due to their biological importance, their fascinating physical, chemical, and spectroscopic properties.1 These compounds have a high electron density due to its 18 π-electrons delocalized on the macrocyclic ring, which are responsible for their spectroscopic characteristics. 2Porphyrin and its derivatives play multiple roles in nature, such as energy transfer and light absorption in a wide range of the electromagnetic spectrum. Such features are of great interest to the industry of optoelectronic components, such as solar cells, due to its ability to act as photosensitizers when irradiated under visible light.3 Thus, this is certainly one of the most promising areas of application for these compounds. The structural modeling and synthesis of new porphyrins has grown exponentially in order to control their electronic and thermal properties. 4 The addition of substituents at the meso positions and metal ions in the center of porphyrins can improve the electrical and magnetic properties, protecting against auto-oxidation and reducing the formation of dimers. However, these structural modifications can promote, in some cases, a significant decrease in their planarity. 5A simple way to obtain porphyrins is the acid catalyzed condensation reaction of pyrrole with specific aldehyde, followed by oxidation of the porphyrinogen. This procedure, originally developed by Rothemund,6 has been refined by [7][8][9] due to the addition of metal salts to the reaction. Despite the modest yields, the relative simplicity of this method has become suited for preparation of large amounts of tetraarylporphyrins. Higher yields an...

show abstract

Section: Characterizationmentioning

confidence: 99%

mentioning

confidence: 99%

Synthesis, Characterization and Dielectric Properties of New 5-(4-Hydroxyphenyl)-10,15,20-tri-4-[2-(3-pentadecylphenoxy)ethoxy]phenyl porphyrin and Their Ni, Co and Cu Complexes

Mota¹,

Júnior²,

Ribeiro³

et al. 2016

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…One-photon excited time-resolved fluorescence measurements (OPE-FLIM) on solid samples were performed on a MicroTime200 time resolved confocal fluorescence microscope system (PicoQuant) coupled with an SR-163 spectrograph and equipped with a Newton 970 EMCCD camera (Andor Technology) previously described [ 25 ]. We used for excitation a laser diode, operating at 485 nm and the signal was filtered by a HQ519LP (Chroma, Foothill Ranch, CA, USA) emission filter.…”

Section: Methodsmentioning

confidence: 99%

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

Stoean

Rugină

Focșan

et al. 2021

IJMS

Self Cite

View full text Add to dashboard Cite

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a’ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a’ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.

show abstract

“…Encompassing our study on the topic of synthesis, metal complexation and optical properties of meso -phenothiazinyl-phenyl porphyrin (MPP) dyes previously reported by our research group [ 31 , 32 ], in this work we introduce a series of additional new MPP derivatives with extended-conjugation π-electron systems brought by peripheral/bridging ethyne auxochrome units capable of inducing favorable steric orientation of the aromatic rings. Their synthesis based on direct one-pot Adler–Longo mixt.…”

Section: Introductionmentioning

confidence: 99%

Ethyne Functionalized Meso-Phenothiazinyl-Phenyl-Porphyrins: Synthesis and Optical Properties of Free Base Versus Protonated Species

et al. 2020

Self Cite

View full text Add to dashboard Cite

Synthesis, structural characterization and photophysical properties for a series of new trans-A2B2- and A3B-type ethynyl functionalized meso-phenothiazinyl-phenyl porphyrin derivatives are described. The new compounds displayed the characteristic porphyrin absorption spectra slightly modified by weak auxochromic effects of the substituents and fluorescence emission in the range of 651–659 nm with 11–25% quantum yields. The changes recorded in the UV-vis absorption spectra in the presence of trifluoroacetic acid (TFA) are consistent with the protonation of the two internal nitrogen atoms of the free-base porphyrin (19 nm bathochromic shift of the strong Soret band and one long wave absorption maxima situated in the range of 665–695 nm). Protonation of the phenothiazine substituents required increased amounts of TFA and produced a distinct hypsochromic shift of the long wave absorption maxima. The density functional theory (DFT) calculations of a porphyrin dication pointed out a saddle-distorted porphyrin ring as the ground-state geometry.

show abstract

Metallo complexes of meso-phenothiazinylporphyrins: Synthesis, linear and nonlinear optical properties

Cited by 16 publications

References 24 publications

Synthesis, Characterization and Dielectric Properties of New 5-(4-Hydroxyphenyl)-10,15,20-tri-4-[2-(3-pentadecylphenoxy)ethoxy]phenyl porphyrin and Their Ni, Co and Cu Complexes

Synthesis, Characterization and Dielectric Properties of New 5-(4-Hydroxyphenyl)-10,15,20-tri-4-[2-(3-pentadecylphenoxy)ethoxy]phenyl porphyrin and Their Ni, Co and Cu Complexes

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

Ethyne Functionalized Meso-Phenothiazinyl-Phenyl-Porphyrins: Synthesis and Optical Properties of Free Base Versus Protonated Species

Contact Info

Product

Resources

About