Synthesis of Ag(II) 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin and its facile demetalation to 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin

2016 ◽  
Vol 20 (05) ◽  
pp. 656-661
Author(s):  
Sasitha Vidyarini Ravindran ◽  
Anuj Krishnasundar Pennathur ◽  
G. Nandhini Devi ◽  
Gautam Pennathur
Keyword(s):  
Mass Spectrometry ◽  
Molecular Weight ◽  
Trifluoroacetic Acid ◽  
Time Interval ◽  
Sodium Sulphide ◽  
Free Base ◽  
H Nmr ◽  
Mild Conditions ◽  
One Step ◽  
Uv Visible

A novel one-step strategy for the synthesis of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin using AgIIOBP is described. AgIIOBP was synthesized and was. Bromination of AgIITPP was carried out in a one-step reaction by varying the subsequently demetalated using H2S time interval and stoichiometric addition of Br2. The molecular weight of the halogenated porphyrin was confirmed by MALDI-TOF mass spectrometry. The synthesis of Ag(II) 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin was followed by demetalation of Ag(II) ion from the halogenated porphyrin. The demetalation of was carried out under mild conditions using sodium sulphide in trifluoroacetic acid. The time taken for the demetalation was considerably lesser than previously reported and which facilitated a simple way for the isolation of the final product in good yield. The yield of the free base was 98%. The formation of the product and purity was confirmed by 1H NMR, Mass spectrometry. UV-visible spectrophotometer clearly showed the appearance of a characteristic Q-band of the octa-brominated porphyrin.

scholarly journals Synthesis, photophysical properties and photodynamic antimicrobial activity of meso 5,10,15,20-tetra(pyren-1-yl)porphyrin and its indium(III) complex

2021 ◽  
pp. A-F
Author(s):  
Jackline Khisa ◽  
Solomon Derese ◽  
John Mack ◽  
Edith Amuhaya ◽  
Tebello Nyokong
Keyword(s):  
Mass Spectrometry ◽  
Antimicrobial Activity ◽  
Fluorescence Quantum Yield ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Intersystem Crossing ◽  
Free Base ◽  
H Nmr ◽  
Solvent Systems ◽  
Dose Dependent

In this study, free-base meso 5,10,15,20-tetra(pyren-1-yl)porphyrin (H2TPyP) and its corresponding indium(III) complex (InClTPyP) were synthesized and characterized on the basis of mass spectrometry, 1H NMR spectroscopy and elemental analysis. InClTPyP was obtained in good yield by treating the free base H2TPyP with indium(III) chloride. Purification of these compounds was achieved through column chromatography using different solvent systems. Metallation of the free base to form a metallo-porphyrin afforded improved photophysical properties. There was a bathochromic shift in wavelength of absorption from the parent free base H2TPyP ([Formula: see text] = 431 nm) to metallated indium(III) complex ([Formula: see text] = 443 nm). The fluorescence quantum yield in H2TPyP was higher ([Formula: see text] = 0.131) than in InClTPyP ([Formula: see text] = 0.017) due to efficient intersystem crossing to the triplet manifold in the metallated porphyrin. Upon illumination, both H2TPyP and InClTPyP show effective dose dependent antimicrobial activity against Staphylococcus aureus with photoinactivation IC[Formula: see text] values of 27.89 and 16.67 [Formula: see text]M, respectively.

Gilded Chalices: Tetra-aurated Calix[4]arenes

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1061-1072 ◽  
Author(s):  
Ulf H. Strasser ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
Raphael J. F. Berger ◽  
Norbert W. Mitzela
Keyword(s):  
Crystal Structure ◽  
Mass Spectrometry ◽  
Quantum Chemical ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Elemental Analyses ◽  
One Step ◽  
Energy Of Formation

Abstract 5,11,17,23-Tetrakis(trimethylsilylethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (1) was synthesised in two steps starting from 25,26,27,28-tetra-n-propoxycalix[4]arene, and the structure of 1 was determined by X-ray diffraction. Compound 1 was desilylated (K2CO3) to give 5,11,17,23- tetrakis(ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (2), which was tetra-aurated under basic conditions (NaOEt, THF) with a series of phosphane-gold chlorides (o-Tol3PAuCl, Ph3PAuCl, Ph2MePAuCl, PhMe2PAuCl, Me3PAuCl, Cy3PAuCl, t-Bu3PAuCl) to afford in good to excellent yields the tetra-aurated tetraethynylcalix[4]arene species 3-9 in one step [with phosphane ligands o-Tol3P (3), Ph3P (4), Ph2MeP (5), PhMe2P (6), Me3P (7), Cy3P (8), t-Bu3P (9)]. All compounds were characterised by 1H NMR and infrared spectroscopy, mass spectrometry and by elemental analyses, additionally 3, 4, 5, 8 and 9 by 13C{1H}, and 3-6, 8 and 9 by 31P{1H} NMR spectroscopy. The molecular structures of complexes 3 and 9 were determined by X-ray diffraction and show pinched-cone conformations, but neither intra- nor intermolecular attractive aurophilic Au···Au contacts. The acceptor ability of complexes 3 and 9 was investigated by complexation attempts with various phosphane-gold chlorides and xenon gas under pressure, but interactions could not be determined experimentally. The formation of a complex between xenon and gilded calix[4]arene could, however, be predicted for fluorine-substituted species and with very small phosphane ligands (PH3) on the basis of quantum-chemical calculations; the energy of formation is 9:6 kJ mol-1. The crystal structure of Ph2MePAuCl was also determined and shows Au···Au-bonded dimers.

Halo-Wittig- and zirconium-promoted synthesis of conjugated metalloporphyrin dimers

2010 ◽  
Vol 14 (04) ◽  
pp. 298-304 ◽  
Author(s):  
Muhammad Yaseen ◽  
Mukhtar Ali ◽  
Munawar Ali Munawar ◽  
Muhammad Salim ◽  
Muhammad NajeebUllah ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Raman Spectroscopy ◽  
Elemental Analysis ◽  
Spectroscopic Studies ◽  
H Nmr ◽  
Uv Visible

The synthesis and spectroscopic studies of metalloporphyrin dimers having 1,3-butadiyne linker attached to the beta pyrrolic positions of the linked porphyrins are reported. Bromoethenyl metalloporphyrins were synthesized by zirconocene-promoted bromomethylenation of beta formyl metalloporphyrins. Bromoethenyl metalloporphyrins were dehydrohalogenated by potassium tert-butoxide to give beta ethynyl or 2-ethynyl metalloporphyrins. It is the first documented example of zirconocene-promoted bromomethylenation of beta formyl metalloporphyrins. Bromoethenyl metalloporphyrins were also synthesized by halo-Wittig route. 2-ethynyl metalloporphyrins were self dimerized to give metalloporphyrin dimers having 1,3-butadiyne linking bridge. FTIR, Raman spectroscopy, UV-visible, elemental analysis, 1H NMR and mass spectrometry were used to characterize the compounds.

Porphyrin-rhodanine dyads for dye sensitized solar cells

2006 ◽  
Vol 10 (08) ◽  
pp. 1007-1016 ◽  
Author(s):  
Lingamallu Giribabu ◽  
Ch. Vijay Kumar ◽  
P. Yella Reddy
Keyword(s):  
Solar Cells ◽  
Dye Sensitized Solar Cells ◽  
Acid Group ◽  
Redox Potentials ◽  
Free Base ◽  
Zinc Porphyrin ◽  
H Nmr ◽  
Dye Sensitized ◽  
Uv Visible ◽  
Sensitized Solar Cells

A series of four new porphyrin-rhodanine dyads were synthesized having the rhodanine acetic acid group either at the meso- or the pyrrole-β position of a free-base/zinc porphyrin. These dyads were fully characterized by UV-visible, 1 H NMR, MALDI-MS and fluorescence spectroscopies and cyclic voltammetry. Both the Soret and Q-bands were red-shifted in the case of pyrrole-β substituted dyads. The redox potentials of all four dyads were altered in comparison with their individual constituents. The dyads were tested in dye sensitized solar cells and the zinc metalated dyads gave a better performance in comparison with the corresponding free-base dyads.

Synthesis of 5,10,15-Tris(4-nitrophenyl)-20-hydroxylphenylporphyrin and its Spectrum Study

2012 ◽  
Vol 549 ◽  
pp. 269-273
Author(s):  
Huan Bao Fa ◽  
Hui Qi ◽  
Wei Yin ◽  
Dan Qun Huo ◽  
Chang Jun Hou
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Fluorescence Intensity ◽  
Trifluoroacetic Acid ◽  
Fluorescence Spectra ◽  
Reaction Conditions ◽  
Ir Spectrometry ◽  
Absorption And Emission ◽  
Novel Method ◽  
Uv Visible

5,10,15-Tris(4-nitrophenyl)-20-hydroxylphenylporph-yrin was synthesized by a novel method which was for the nitration of the phenyl groups of 5-(4-hydroxylphenyl)-10,15,20- triphenylporphyin(MHTPP) using NaNO2 and trifluoroacetic acid(TFA) and characterized using mass spectrometry, NMR spectroscopy, UV-visible, IR spectrometry. The mild reaction conditions produced higher yields and minimum macrocyclic degradation. Its fluorescence spectra was studied compared with MHTPP and tetraphenylporphyrin(TPP). The results showed that the absorption and emission bands of the product experienced red shifts and the fluorescence intensity weakened compared with MHTPP and TPP.

Synthesis, structure and spectroscopic properties of a porphycene-ReI complex

2011 ◽  
Vol 15 (07n08) ◽  
pp. 622-631 ◽  
Author(s):  
Weina Zhang ◽  
Yi Chang ◽  
Fan Wu ◽  
John Mack ◽  
Nagao Kobayashi ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Single Crystal ◽  
Spectroscopic Properties ◽  
Free Base ◽  
X Ray ◽  
H Nmr ◽  
New Type ◽  
Uv Visible ◽  
C Nmr

A new type of rhenium(I) tricarbonyl porphycene complex is reported based on a reaction between free-base 2,3,6,7,12,13,16,17-octaethylporphycene (H2OEPc) and Re(CO)5Cl . As is the case with tetraphenylporphyrin (TPP), a complex containing only one Re(CO)3 groups, which retains a pyrrole proton, can be isolated and characterized in addition to a bis- Re(I) complex. The ReI(HOEPc)(CO)3 complex was characterized by 1H NMR, 13C NMR, MS, IR, UV-visible, and MCD spectroscopy and cyclic voltammetry. A single crystal was successfully obtained, which enabled the determination of the X-ray structure.

Synthesis of α,ω-bis(3-aminopropyldiethoxylsilane) Poly(tri fluoropropylmethyl)siloxanes

e-Polymers ◽  
2007 ◽  
Vol 7 (1) ◽  
Author(s):  
Zhendong Shi ◽  
Xinling Wang
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Reaction Rate ◽  
Ring Opening Polymerization ◽  
Step Process ◽  
Molecular Weights ◽  
H Nmr ◽  
One Step ◽  
Ft Ir ◽  
High Yields

AbstractHigh molecular weight α,ω-bis(3-aminopropyldiethoxylsilane) poly(tri fluoropropylmethyl)siloxanes (APTFPMS) were prepared via a “one-step” process, based on the ring-opening polymerization of 1,3,5-tris(trifluoropropylmethyl) cyclotrisiloxane (F3) in the presence of water and 3-aminopropyltriethoxysilane (APTES). GPC, FT-IR and 1H NMR confirmed the structure of the polymers. It was found that the amount of APTES had significant influence on the reaction rate and the molecular weights of polymers decreased with the increasing amount of water. It was probably because both water and the amino group of APTES favoured generation of hydroxyl ions, which efficiently initiate the polymerization of F3 to achieve APTFPMS. In order to verify this mechanism, another “two-step” process was also performed: Firstly the α,ω-dihydroxylated poly(trifluoropropylmethyl) siloxanes were synthesized from F3 catalyzed by both diaminoethane and water, then reacted with APTES to achieve APTFPMS. All the syntheses had high yields and the molecular weight of the polymers ranged from 2000 to 25000.

Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety

2015 ◽  
Vol 19 (07) ◽  
pp. 819-829 ◽  
Author(s):  
Xu Liang ◽  
Li Xu ◽  
Minzhi Li ◽  
John Mack ◽  
Justin Stone ◽  
...  
Keyword(s):  
Electronic Structures ◽  
Magnetic Circular Dichroism ◽  
Theoretical Calculations ◽  
Free Base ◽  
Facile Synthesis ◽  
Visible Absorption ◽  
H Nmr ◽  
Uv Visible ◽  
Porphyrin Dimers ◽  
Porphyrin Dimer

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 1 H 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.

Sign in / Sign up

Export Citation Format

Share Document