Far-red absorbing azodipyrrin dyes — Synthesis, X-ray crystallographic, and spectral characterization of 1,9-diazodipyrrins and their metal complexes

2011 ◽  
Vol 89 (4) ◽  
pp. 481-487 ◽  
Author(s):  
Yan Li ◽  
David Dolphin
Keyword(s):  
Metal Complexes ◽  
Zinc Complex ◽  
Nickel Complexes ◽  
Crystallographic Analysis ◽  
Zinc Complexes ◽  
Spectral Characterization ◽  
X Ray ◽  
Almost All ◽  
C Nmr

A series of novel 1,9-diazodipyrrins (4) were readily synthesized by reacting aryldiazonium salts with 5-aryldipyrromethanes under both acidic and basic conditions. The zinc complex of 1,9-diphenylazodipyrrin (5aZn) was confirmed by X-ray crystallographic analysis, and 1,9-diazodipyrrins and their zinc and nickel complexes (5M) were characterized by 1H and 13C NMR, IR, UV–vis, and MS. All of the metal complexes absorb almost all colours of the rainbow; the absorption maximums are >650 nm and the half-band widths are over 100 nm. The fluorescence of the zinc complexes of 1,9-diphenylazodipyrrin (5aZn) and 1,9-di(2-iodophenylazo)dipyrrin (5cZn) were also explored.

Selenium coronands. A novel conformational pair

1988 ◽  
Vol 66 (11) ◽  
pp. 2956-2958 ◽  
Author(s):  
B. Mario Pinto ◽  
Blair D. Johnston ◽  
Raymond J. Batchelor ◽  
Frederick W. B. Einstein ◽  
Ian D. Gay
Keyword(s):  
Nmr Spectra ◽  
Crystallographic Analysis ◽  
The Novel ◽  
Torsion Angles ◽  
X Ray ◽  
Structure Formula ◽  
Independent Molecules ◽  
Similar Conformation ◽  
C Nmr

The synthesis and characterization of the novel selenium coronands, 1,3,7,9-tetraselenacyclododecane 1a, 1,3,7,9,13,15-hexaselenacyclooctadecane 2a, the corresponding β-gem-dimethyl derivatives 1b, 2b, and 1,5,9,13-tetraselenacyclohexadecane 3, and 1,5,9,13,17,21-hexaselenacyclotetracosane 4 are described. X-ray crystallographic analysis of 1a reveals three independent molecules that exist in two distinct conformations, one molecule having approximate two-fold symmetry together with two molecules (of similar conformation) each having crystallographic [Formula: see text] symmetry. The conformations are denoted as [3333] or [66]. Whereas one resembles that of cyclododecane and tetrathia-12-crown-4 with respect to torsion angles, the other resembles that of tetraoxa-12-crown-4. The solid state CP-MAS 77Se and 13C nmr spectra are interpreted in light of the crystallographic information. Crystal structure: formula Se4C8H16; fw = 428.05; monoclinic, P21/c; Z = 8; a = 15.823(2) Å, b = 5.534(1) Å, c = 27.962(5) Å, β = 92.26(1)°; V = 2446.6 Å3; T = 200 K; R = 0.027 for 2162 observed data (I ≥ 2.5σ(I)).

Synthesis and characterization of novel azo-embedded N-confused tetraphenylporphyrin

2009 ◽  
Vol 13 (02) ◽  
pp. 215-222 ◽  
Author(s):  
Motoki Toganoh ◽  
Takayoshi Hihara ◽  
Kentaro Yonekura ◽  
Yuichi Ishikawa ◽  
Hiroyuki Furuta
Keyword(s):  
Absorption Spectrum ◽  
Effective Interaction ◽  
Coupling Reaction ◽  
Crystallographic Analysis ◽  
Synthesis And Characterization ◽  
X Ray ◽  
H Nmr ◽  
Cis Isomer ◽  
C Nmr

A unique class of azo porphyrin, 5,10,15,20-tetraphenyl-21-phenylazo-(2-aza-21-carbaporphyrin 1, in which an azophenyl group is embedded in N -confused porphyrin, was synthesized and characterized by 1 H NMR, 13 C NMR, UV-vis absorption, MS, and X-ray crystallographic analysis. Synthesis of 1 was achieved through a coupling reaction of 21-amino N -confused tetraphenylporphyrin with nitrosobenzene and subsequent deoxygenation of resulting azoxy derivative with a trioxo rhenium(VII) N -fused porphyrinato catalyst. The azo-conjugate molecule was exclusively obtained as a trans-isomer and no isomerization to the cis-isomer was observed under thermal or photoirradiation. The absorption spectrum of 1 shows a moderate red-shift due to the effective interaction between the porphyrinic π-system and the connecting azophenyl group. Upon protonation, this effect is essentially lost as a result of removing degeneracy of LUMO and LUMO+1.

Electrochemistry of nickel picket fence porphyrin. Electrogeneration and spectral characterization of nickel complexes in unusual oxidation states

1989 ◽  
Vol 28 (13) ◽  
pp. 2542-2547 ◽  
Author(s):  
K. M. Kadish ◽  
D. Sazou ◽  
G. B. Maiya ◽  
B. C. Han ◽  
Y. M. Liu ◽  
...  
Keyword(s):  
Nickel Complexes ◽  
Spectral Characterization ◽  
Oxidation States ◽  
Picket Fence

scholarly journals Characterization of reactive organometallic species via MicroED

2019 ◽  
Author(s):  
Christopher Jones ◽  
Matthew Asay ◽  
Lee Joon Kim ◽  
Jack Kleinsasser ◽  
Ambarneil Saha ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Cryogenic Cooling ◽  
Structural Determination ◽  
X Ray ◽  
X Ray Crystallography ◽  
Diamagnetic Transition

Here we apply microcrystal electron diffraction (MicroED) to the structural determination of transition metal complexes. We find that the simultaneous use of 300 keV electrons, very low electron doses, and an ultra-sensitive camera allows for the collection of data without cryogenic cooling of the stage. This technique reveals the first crystal structures of the classic zirconocene hydride, colloquially known as “Schwartz’s reagent”, a novel Pd(II) complex not amenable to solution-state NMR or X-ray crystallography, and five other paramagnetic or diamagnetic transition metal complexes.

Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1601-1608 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Nickel Complexes ◽  
Addition Reactions ◽  
Coordination Geometry ◽  
X Ray ◽  
Square Planar ◽  
Structure Determinations

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.

Spectral characterization of flash and high flux x-ray radiographic sources with a magnetic Compton spectrometer

2021 ◽  
Vol 92 (8) ◽  
pp. 083102
Author(s):  
M. Espy ◽  
M. Klasky ◽  
M. James ◽  
D. Moir ◽  
J. Mendez ◽  
...  
Keyword(s):  
Spectral Characterization ◽  
High Flux ◽  
X Ray

New Macrocyclic Complexes Derived From Cobalt(III) Cage Complexes

1994 ◽  
Vol 47 (3) ◽  
pp. 529 ◽  
Author(s):  
II Creaser ◽  
T Komorita ◽  
AM Sargeson ◽  
AC Willis ◽  
K Yamanari
Keyword(s):  
Aqueous Solution ◽  
Strain Energy ◽  
Macrocyclic Ligand ◽  
Zinc Powder ◽  
Crystallographic Analysis ◽  
X Ray ◽  
Alkyl Complexes ◽  
Nitrogen Donor ◽  
Asymmetric Nitrogen

The synthesis and partial characterization of several green complexes, derived from the products of the reactions between [Co(Cl2-sar)]3+ (Cl2-sar = 1,8-dichloro-3,6,10,13,16,19- hexaazabicyclo [6.6.6] icosane ) and zinc powder in water, are described. Most of the complexes appear to have [CoCl2(N4)] chromophores , where N4 denotes the tetraaza macrocyclic ligand , 6,13-dimethylene-1,4,8,11-tetraazacyclotetradecane (L1). For trans-[CoCl2(L1)]+, three isomers due to different configurations about the asymmetric nitrogen donor centres were obtained and characterized by the electronic absorption and 13C n.m.r. spectra. Their stereochemistry is discussed and compared with that of 1,4,8,11-tetraazacyclotetradecane on the basis of strain energy minimized calculations. A trans-[CoCl2(H2L2)]3+ complex containing a related macrocycle with a pendant ethane-1,2-diamine arm [H2L2+, 6-(4-ammonio-2-azoniabutyl)-13-methylene-1,4,8,11-tetraazacyclotetradecane] was also isolated and characterized by X-ray crystallographic analysis. All these molecules are derived from the decomposition of zinc alkyl complexes formed by oxidative addition of zinc to the parent [CoII(Cl2-sar)]2+ ion in aqueous solution.

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