Synthesis and characterization of meso-to-meso directly linked porphyrin-diazaporphyrin triads

2018 ◽  
Vol 22 (09n10) ◽  
pp. 814-820
Author(s):  
Yingying Jia ◽  
Ling Xu ◽  
Bangshao Yin ◽  
Mingbo Zhou ◽  
Jianxin Song
Keyword(s):  
Nickel Complex ◽  
High Resolution Mass Spectrometry ◽  
Dihedral Angles ◽  
X Ray Diffraction ◽  
Extinction Coefficients ◽  
X Ray ◽  
H Nmr ◽  
First Time ◽  
Molar Extinction Coefficients

Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of reactions including formylation via Vilsmeier–Haack reaction, condensation with pyrrole, bromination with [Formula: see text]-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), metal-templated cyclization of dibromodipyrrin-metal complexes with NaN[Formula: see text] and demetalization. All these triads were comprehensively characterized by [Formula: see text]H NMR, high-resolution mass spectrometry and UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)[Formula: see text] between each mean plane of porphyrin and that of central diazaporphyrin The UV-vis absorption spectra disclosed that the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm, respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin monomers reported previously the molar extinction coefficients, particularly for triad 8Ni are much higher.

Spectroscopic and X-Ray Investigation of Cobalt(III) Complexes with 2-Oximinocarboxylic Acids

1993 ◽  
Vol 48 (4) ◽  
pp. 409-417 ◽  
Author(s):  
Rostislav D. Lampeka ◽  
Zamira D. Uzakbergenova ◽  
Victor V. Skopenko
Keyword(s):  
Electronic Absorption Spectra ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Octahedral Structure ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
R Factors

Mixed complexes of Co(III) with 2-oximinopropionic (H2A) or 2-oximino-3-phenylpropionic (H2B) acid and different amine (imidazole, benzimidazole, pyridine, β-picoline, γ-picoline) are reported. Characterization of the complexes was based upon elemental analysis, conductivity and JR, 1H NMR, and electronic absorption spectra, and X-ray diffraction analysis. The organic ligands behave as O,N donors via the carboxyl oxygen and the oxime nitrogen atoms. A trans-octahedral structure has been assigned to the bis(2-oximinocarboxylato)bis(amine)cobalt(III) on the basis of 1H NMR data.The crystal and molecular structures of the complexes trans-[bis(2-oximinopropionato)bis-(imidazole)]- (I) and trans-[bis(2-oximinopropionato)bis(pyridine)]cobalt(III) (II) were determined. I crystallizes in space group P2/n with a = 14.1 67(2), b = 8.774(1), c = 14.785(2) Å,β = 113.37(1)°, Z = 4, Dcalc = 1.568 g · cm-3. II crystallizes in space group P1̄ with a = 9.122(2), b = 10.038(2), c = 11.759(2) Å, α = 69.95(1)°, β = 67.47(2)°, γ = 69.49(2)°, Ζ = 2, Dcalc = 1.547 g cm-3. The structures were refined to unweighted R factors of 0.036 and 0.028, respectively. The coordination sphere around Co is pseudo-octahedral with the 2-oximinopropionato ligands occupying four equatorial positions, and the amines in axial positions.

Synthesis and Electrochemistry of Aluminum Porphycenes: Crystal and Molecular Structure of Methyl-σ-Bonded Aluminum Etioporphycene

1997 ◽  
Vol 01 (02) ◽  
pp. 109-119 ◽  
Author(s):  
ROGER GUILARD ◽  
VIRGINIE PICHON-PESME ◽  
HASSANE LACHEKAR ◽  
CLAUDE LECOMTE ◽  
ALLY M. AUKAULOO ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Structural Data ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Axial Ligands ◽  
Uv Visible

The synthesis and characterization of three monomeric aluminum porphycenes with anionic or σ-bonded axial ligands is reported. The investigated compounds are represented as ( EtioPc ) Al ( CH 3) and ( EtioPc ) AlX where EtioPc represents the dianion of etioporphycene and X = Cl − or OH −. Each synthesized complex was characterized by mass spectrometry. 1 H NMR, IR and UV-visible spectroscopies as well as by electrochemistry. Comparisons are made between the properties of complexes in the aluminum etioporphycene series and related chloro- or methyl σ-bonded Al ( III ) porphyrins containing octaethylporphyrin ( OEP ) or tetraphenylporphyrin ( TPP ) macrocycles. Comparisons are also made between the currently investigated compounds and a previously reported Al ( III ) μ-oxo dimer, [( EtioPc ) Al ]2 O . In addition, the crystal and molecular structure of ( EtioPc ) Al ( CH 3) was determined by X-ray diffraction. The molecular structure of this methyl-σ-bonded aluminum etioporphycene provides the first structural data for an aluminum porphycene compound. The aluminum(III) atom in ( EtioPc ) Al ( CH 3) is pentacoordinated and is located 0.54 Å from the plane of the four N -nitrogens.

Synthesis and Characterization of a Dumbbell-Shaped Polyrotaxane Based on Polytetrahydrofuran bis(3-aminopropyl) Terminated and α-Cyclodextrins Using Polyamidoamine (PAMAM) Dentrimers as Bulky Stoppers

2015 ◽  
Vol 1094 ◽  
pp. 41-48
Author(s):  
Ri Min Cong ◽  
Huai Qing Yu ◽  
Yan Gong Yang ◽  
Si Yi Yang ◽  
Jiao Li ◽  
...  
Keyword(s):  
Thermogravimetric Analysis ◽  
Inclusion Complex ◽  
Inclusion Complexes ◽  
Synthesis And Characterization ◽  
Wide Angle ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Channel Type

A dumbbell-shaped polyrotaxane based on polytetrahydrofuran bis (3-aminopropyl) terminated and α-cyclodextrins using polyamidoamine (PAMAM) dentrimers as bulky stoppers was successfully prepared. The1H NMR results show that the peaks of α-CDs in these polyrotaxanes are broadened compared with pure α-CDs. Wide-angle X-ray diffraction (XRD) measurements of the resulting polyrotaxanes suggest to produce a channel-type crystalline structure of inclusion complex. Thermogravimetric analysis (TGA) of the resultant polyrotaxanes show that α-CDs are significantly stabilized by the formation of the inclusion complexes.

scholarly journals Lactide polymerization with iron alkoxide complexes

2015 ◽  
Vol 93 (6) ◽  
pp. 594-601 ◽  
Author(s):  
Arek Keuchguerian ◽  
Berline Mougang-Soume ◽  
Frank Schaper ◽  
Davit Zargarian
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Side Reactions ◽  
X Ray Diffraction ◽  
Iron Cluster ◽  
X Ray ◽  
H Nmr ◽  
Exchange Product

This report presents the results of a study on the preparation of iron alkoxide complexes chelated by diiminopyridine ligands and their role in the room temperature polymerization of rac-lactide. Reaction of N,N′-(p-R-C6H4CH2)2-diiminopyridines (R = H (1), F (2)) with FeX2 (X = Cl, Br) yielded the homoleptic complexes [(1)2Fe][FeX4] or [(2)2Fe][FeX4], respectively. Treating the latter with Na[BPh4] afforded the anion exchange product [(2)2Fe][BPh4]2, which was characterized by 1H NMR and absorption spectroscopy, combustion analysis, and single crystal X-ray diffraction. Various attempts to grow crystals of [(1)2Fe][FeX4] and [(2)2Fe][FeX4] culminated in the isolation of single crystals of [(2)2Fe][Cl6Fe2O] that was characterized by X-ray diffraction. Attempted synthesis of well-defined, mononuclear alkoxide derivatives from [(1)2Fe]2+ or [(2)2Fe]2+ gave mostly intractable products, but in one case we obtained the crystallographically characterized sodium iron cluster Na4Fe2(OC6H4F)8(THF)2. An aryloxide derivative proved accessible by reaction of NaOC6H4F with the mono-ligand precursor LFeCl2 (L = N,N′-dimesityl-diiminopyridine), but characterization of LFe(OC6H4F)2 was limited to a single crystal X-ray diffraction analysis, owing to unsuccessful attempts at isolating pure samples. The difficulties encountered in the isolation of pure alkoxide derivatives prompted us to use in-situ generated LFe(OEt)2 for studying the polymerization of rac-lactide. This system was found to be moderately active at room temperature and with a slight preference for the formation of a heterotactic polymer (Pr = 0.54–0.65). Large polydispersities of 1.5–2.0 indicated the presence of transesterification side-reactions, which were confirmed by the presence of peaks with m/z = n 144 + M(EtOH) + M(Na+) and m/z = (n + 0.5) 144 + M(EtOH) + M(Na+) in MALDI-MS.

Synthesis and Characterization of CeO2 Nanoparticles

2016 ◽  
Vol 683 ◽  
pp. 281-287 ◽  
Author(s):  
Ivan N. Lapin ◽  
Anastasiia V. Shabalina ◽  
Valery Svetlichnyi
Keyword(s):  
Cerium Oxide ◽  
Ethanol Solution ◽  
Nanocrystalline Powders ◽  
X Ray Diffraction ◽  
Active Components ◽  
X Ray ◽  
Average Size ◽  
First Time ◽  
Metallic Target

Dispersions of cerium oxide nanoparticles in water, ethanol, and water-ethanol solution were synthesized for the first time using laser ablation of metallic target. The fundamental harmonic of nanosecond Nd:YAG laser was used. Nanocrystalline powders of cerium oxide were obtained from the dispersions. The average size of the crystallites was 17-19 nm. Phase composition of nanoparticles was confirmed by X-ray diffraction and Raman spectroscopy. It was found that carbon present on the surface of CeO2 particles. The materials obtained may be used as catalyst carriers for CO oxidation, and as active components of sunscreen cosmetic products.

scholarly journals Synthesis and Molecular Structure of 4′,9′,4″,9″-Tetra-tert-butyl-1′,6′,1″,6″-tetramethoxy-2,5-dioxa[3.3]metabiphenylophane

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
Tetsuji Moriguchi ◽  
Tatsuya Egami ◽  
Akihiko Tsuge
Keyword(s):  
Molecular Structure ◽  
Condensation Reaction ◽  
Solvent Molecule ◽  
Dihedral Angles ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cell Parameters ◽  
H Nmr ◽  
Crystal Space

A large calixarene-like metacyclophane, 4′,9′,4″,9″-tetra-tert-butyl-1′,6′,1″,6″-tetramethoxy-2,5-dioxa[3.3]metabiphenylophane, was synthesized by an intermolecular condensation reaction of its corresponding bischloromethyl-biphenyl and bishydroxymethyl-biphenyl precursors. After molecular characterization by 1H NMR spectroscopy and mass spectrometry, the compound generated single crystals by recrystallization from a dichloromethane/hexane mixture, facilitating an exact conformational determination via X-ray diffraction analysis. The crystal was found to belong to the monoclinic space group P21/n with cell parameters a = 19.908(2) Å, b = 9.7193(11) Å, c = 23.350(3) Å, β = 109.594(1)°, and Dcalc=1.150 g/cm3 at 90 K. The compound adopted quite strained 1,2-alternate-like conformations because its biphenyl parts displayed large dihedral angles and rigidity. The crystal did not incorporate any solvent molecule but its molecular cavity and crystal space were effectively filled by the substituents.

scholarly journals Sustainable Nanotechnologies for Curative and Preventive Wood Deacidification Treatments: An Eco-Friendly and Innovative Approach

Nanomaterials ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 1744
Author(s):  
Giuliana Taglieri ◽  
Valeria Daniele ◽  
Ludovico Macera ◽  
Ralf Schweins ◽  
Sandro Zorzi ◽  
...  
Keyword(s):  
Small Angle Neutron Scattering ◽  
Large Scale ◽  
Alkaline Ph ◽  
X Ray Diffraction ◽  
Satisfactory Solution ◽  
X Ray ◽  
Atomic Force ◽  
Ancient Wood ◽  
First Time

Waterlogged wooden artifacts represent an important historical legacy of our past. They are very fragile, especially due to the severe phenomenon of acidification that may occur in the presence of acid precursors. To date, a satisfactory solution for the deacidification of ancient wood on a large scale has still not been found. In this paper, we propose, for the first time, eco-friendly curative and preventive treatments using nanoparticles (NPs) of earth alkaline hydroxides dispersed in water and produced on a large scale. We present the characterization of the NPs (by X-ray diffraction, atomic-force and electron microscopy, and small-angle neutron scattering), together with the study of the deacidification efficiency of our treatments. We demonstrate that all our treatments are very effective for both curative and preventive aims, able to assure an almost neutral or slightly alkaline pH of the treated woods. Furthermore, the use of water as a solvent paves the way for large-scale and eco-friendly applications which avoid substances that are harmful for the environment and for human health.

Preparation and Characterization of Nickel Complex [Ni(1-MeIm)6(BF4)2] in Ionic Liquid

2010 ◽  
Vol 663-665 ◽  
pp. 1167-1170
Author(s):  
Jun Sai Sun ◽  
Cun Ying Xu
Keyword(s):  
Ionic Liquid ◽  
Nickel Complex ◽  
Phase Method ◽  
Nanometer Scale ◽  
X Ray Diffraction ◽  
X Ray ◽  
Sem Image ◽  
Longitudinal Size ◽  
Solution Phase Method

Nickel complex [Ni(1-MeIm)6(BF4)2, 1-MeIm = 1-methylimidazole] has been prepared in 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4) ionic liquid by a simple solution phase method. The complex was characterized by elemental analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared absorption spectroscopy (IR) and thermal analysis. SEM image indicates that the complex is irregular platelets with an uneven thickness in nanometer scale and variable transverse and longitudinal size, from 0.6 to 4 μm.

Oxazoline chemistry — Part IV: Synthesis and characterization of oxazoline complexes of the zinc halides

2003 ◽  
Vol 81 (12) ◽  
pp. 1482-1491 ◽  
Author(s):  
Tosha M Barclay ◽  
Ignacio del Río ◽  
Robert A Gossage ◽  
Sarah M Jackson
Keyword(s):  
Crystal Structure ◽  
Structural Diversity ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
Zinc Compounds ◽  
X Ray ◽  
H Nmr ◽  
Oxazoline Ligands

The synthesis and characterization of 11 zinc halide derivatives that contain monodentate oxazoline ligands is described. The treatment of ether solutions of [ZnX2] (X = Cl, Br, I) with 2-aryl- or 2-methyl-2-oxazolines results in the formation of mildly hygroscopic complexes of the general formulae [ZnX2(ox)2] (ox = 2-methyl-2-oxazoline (1), 2,4,4-trimethyl-2-oxazoline (2), 2-phenyl-2-oxazoline (3), or 4,4-dimethyl-2-phenyl-2-oxazoline (4)), except in the case of ZnI2, which does not form an isolable complex — likely for steric reasons — with oxazoline 4. Treatment of [ZnBr2(4)2] with 1 reveals (1H NMR) that 1 only sluggishly displaces coordinated 4 at temperatures below 50 °C. The structural characterization, via single crystal X-ray diffraction, of six of the complexes, viz. [ZnI2(1)2], [ZnI2(2)2], [ZnX2(3)2] (X = Cl, Br, or I), and [ZnBr2(4)2], is also reported. All of these structurally characterized complexes are mononuclear zinc compounds with an overall distorted tetrahedral arrangement of the two halide and two oxazoline ligands around the zinc metal centre. The oxazoline series of complexes reported herein show little structural diversity, a facet which is in contrast to their substituted pyridine analogues.Key words: oxazoline, zinc, X-ray crystal structure, coordination complex, NMR spectroscopy, Zn(II).

Synthesis and characterization of a hexaphyrin(1.0.1.0.0.0) bearing both meso- and β-substituents

2007 ◽  
Vol 11 (04) ◽  
pp. 287-293 ◽  
Author(s):  
Jonathan L. Sessler ◽  
Patricia J. Melfi ◽  
Vincent M. Lynch
Keyword(s):  
Crystal Structure ◽  
Ring Current ◽  
Spectroscopic Studies ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Planar Conformation ◽  
Hydrogen Bound

The synthesis of an isoamethyrin-type expanded porphyrin bearing both meso- and β-substituents is presented. The diprotonated form of this macrocycle was characterized by conventional spectroscopic means and via a single crystal X-ray diffraction analysis. This species is observed to adopt a planar conformation in the solid state. Nonetheless, the inner ring current, as inferred from 1 H NMR spectroscopic studies, is found to be severely diminished as compared to isoamethyrin, by the presence of the two meso-phenyl moieties. A second crystal structure, in which a molecule of water is hydrogen-bound to a pyrrole NH , was also solved.

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