131214-90-9

Upstream product

• 128-08-5 N-Bromosuccinimide 
• 14172-92-0 5,10,15,20-tetraphenylporphinatonickel(II) 
• 917-23-7 5,15,10,20-tetraphenylporphyrin 
• 14172-92-0 (tetraphenylporphyrinato)nickel(II) 
• 7558-02-3 potassium bromide 
• 6018-89-9 nickel(II) acetate tetrahydrate 

Relevant academic research and scientific papers

Comparative study of structure-properties relationship for novel β-halogenated lanthanide porphyrins and their nickel and free bases precursors, as a function of number and nature of halogens atoms

The synthetic route of partially β-halogenated via a metal-assisted reaction and perhalogenated terbium complexes is described. This protocol allows the facile insertion of the halogens (bromines or chlorides) to the porphyrin peripheral positions. The electronic absorption spectra and the redox potentials of the free porphyrins as well as the terbium complexes are dramatically affected as the number of halogen atoms increase. In fact, two antagonistic effects are responsible for that, the inductive and the distortion effects on the porphyrin ring. They result in a red shift for the Soret band and a stabilization/destabilization of the HOMOs/LUMOs which in turn is manifested by variations on the redox potentials. The novel crystal structure of the Ni(Cl8TPP) is discussed in great detail and compared with the previously reported structures of Tb(Cl8TPP) (OAc)(DMSO)2·3PhCH3·MeOH and H2(Br8TPP), as well as with other perhalogenated nickel porphyrins available in the literature.

Partial and full β-bromination of meso-tetraphenylporphyrin: Effects on the catalytic activity of the manganese and nickel complexes for photo oxidation of styrene in the presence of molecular oxygen and visible light

A series of β-brominated meso-tetraphenylporphyrins, H2TPPBrx (x = 0, 4, 8) have been synthesized and the photocatalytic activity of their manganese (III) and nickel (II) complexes in photo oxidation of styrene was thoroughly investi

Bromination of tetrapyrrolic scaffolds: A sustainable approach

A sustainable procedure developed for the bromination of organic substrates, such as olefins and small aromatic rings, has been applied to porphyrin derivatives. The synthetic method, based on a V(v) or Mo(vi) catalyzed reaction, occurs in a two-phase med

Synthesis and spectral properties of β-bromo-substituted nickel(II) tetraphenylporphyrins

Bromination of (5,10,15,20-tetraphenylporphyrinato)nickel(II) with N-bromosuccinimide in chloroform and chloroform–dimethylformamide mixture and complexation of 2-bromo-5,10,15,20-tetraphenylporphyrin and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyr

OPTICAL MATERIAL AND USE THEREOF

An optical material of the present invention has a minimum transmittance value in a wavelength range of 445 nm to 470 nm of a transmittance curve measured at a thickness of 2 mm of the optical material.

Comparative study of the catalytic activity of a series of β-brominated Mn-porphyrins in the oxidation of olefins and organic sulfides: Better catalytic performance of the partially brominated ones

The oxidation of olefins and organic sulfides with tetra-n-butylammonium periodate (TBAP) in the presence of a Mn(III) complex from a series of partially and fully brominated meso-tetraphenylporphyrins, MnTPPBrx(OAc) (x = 0, 2, 4, 6 and 8) has been studied in a comparative manner. With the exception of MnTPPBr2(OAc), the half-wave potential for the Mn(III)/Mn(II) metal-centered process was gradually shifted to higher values on going from MnTPP(OAc) to MnTPPBr8(OAc). However, a complex order has been observed for the catalytic activity of the complexes; while the stability of the Mn-porphyrins towards oxidative degradation under the reaction conditions decreases in the order MnTPPBr8(OAc) > MnTPP(OAc) > MnTPPBr6(OAc) > MnTPPBr2(OAc) > MnTPPBr 4(OAc), their catalytic activity has been found to follow the order MnTPPBr8(OAc) ? MnTPP(OAc) ≤ MnTPPBr6(OAc) 2(OAc) ≤ MnTPPBr4(OAc). The maximum conversion (42%) was obtained in the case of MnTPPBr4(OAc) and the minimum conversion (14%) is related to MnTPPBr8(OAc). Oxidation of methyl phenyl sulfide with TBAP in a 1:1 molar ratio leads to the following pattern of catalytic activity for the used Mn-porphyrins: MnTPPBr4(OAc) > MnTPP(OAc) > MnTPPBr2(OAc) ≥ MnTPPBr6(OAc) ? MnTPPBr8(OAc). The highest methyl phenyl sulfide conversion is 69% at room temperature.

First X-ray crystal structure of a lanthanide(III) monoporphyrinic complex using non-planar porphyrin rings

Twenty-three years after the first synthesis of lanthanide(III) porphyrins the X-ray crystal structure of [TbIII(β-Cl8tpp)(O2CMe)(Me 2SO2] is reported; the synthetic route to four halogenated porphyrins H2(β-Xntpp) (X = Cl or Br, n = 4 or 8) is described and compared with the corresponding [TbIII(β-Xntpp)(O2CMe)]; the highly distorted structure of the TbIII complex is compared with similar perhalogenated porphyrinic complexes; the X-ray structure of the brominated free base is also reported.

Octabromotetraphenylporphyrin and its metal derivatives: Electronic structure and electrochemical properties

The free-base octabromotetraphenylporphyrin (H2OBP) has been prepared by a novel bromination reaction of (meso-tetraphenylporphyrinato)copper(II). The metal [VIVO, Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Ag(II), Pt(II)] derivatives exhibit interesting electronic spectral features and electrochemical redox properties. The electron-withdrawing bromine substituents at the pyrrole carbons in H2OBP and M(OBP) derivatives produce remarkable red shifts in the Soret (50 nm) and visible bands (100 nm) of the porphyrin. The low magnitude of protonation constants (pK3 = 2.6 and pK4 = 1.75) and the large red-shifted Soret and visible absorption bands make the octabromoporphyrin unique. The effect of electronegative bromine substituents at the peripheral positions of the porphyrin has been quantitatively analyzed by using the four-orbital approach of Gouterman. A comparison of MO parameters of MOBP derivatives with those of the meso-substituted tetraphenylporphyrin (M(TPP)) and unsubstituted porphine (M(P)) derivatives provides an explanation for the unusual spectral features. The configuration interaction matrix element of the M(OBP) derivatives is found to be the lowest among the known substituted porphyrins, indicating delocalization of ring charge caused by the increase in conjugation of p orbitals of the bromine onto the ring orbitals. The electron-transfer reactivities of the porphyrins have been dramatically altered by the peripheral bromine substituents, producing large anodic shifts in the ring and metal-centered redox potentials. The increase in anodic shift in the reduction potential of M(OBP)s relative to M(TPP)s is found to be large (550 mV) compared to the shift in the oxidation potential (300 mV). These shifts are interpreted in terms of the resonance and inductive interactions of the bromine substituents.