Pyrrole Pigments Research Articles

Novel 2,5-bis(6-(trimethylamonium)hexyl)-3,6-diaryl-1,4-diketopyrrolo[3,4-c]pyrrole pigments as levelers for efficient electroplating applications

2,5-Bis(6-(trimethylamonium)hexyl)-3,6-diaryl-1,4-diketopyrrolo [3,4-c]pyrrole (DPP) pigments are excellent choices as levelers for copper electrodeposition. Herein, novel 4-methoxylaryl (1b) and 4-trifluoromethoxyaryl (1d) diketopyrrolopyrrole-based levelers were synthesized and the inhibitory ability of these levelers is evaluated by electrochemical measurements on copper electrodeposition which were compared with 4-methylaryl (1a) and 4-trifluoromethylaryl (1c) diketopyrrolopyrrole-based levelers. To investigate interactions between metal surface and additives, quantum chemical calculations and molecular dynamics simulations were used. Among them, the 4-trifluoromethoxy-DPP (1d) showed optimal inhibition and strong adsorption capacity on the copper surface. Then, as the representative leveler, 1d was selected for the systematic study of the leveling influence during microvia filling. Notably, 1d has achieved the bottom-up deposition of microvias under the synergistic effect of the microvia filling performance reached 96.9%. These results demonstrated that 1d could serve as a promising leveler for microvia filling and provide theoretical guidance to the discovery and synthesis of novel levelers.

Reactivity of pyrrole pigments, XXI: Structure and reactivity of Cu(II) and Zn(II) bilindione chelates

Several Mn, Cu, and Zn chelates of etiobiliverdin-IV-γ, mesobiliverdin-IXα, and its dimethyl ester are studied. The results show that the chemical constitution of the Cu biliverdin chelate corresponds to a formal metal oxidation state of (II) coordinated to a neutral radical of the NH trideprotonated biliverdin. The reactivity of the Cu(II) bilindione chelates in nucleophilic solvents agrees with that expected for a π neutral radical structure of the ligand; in CH3OH, they undergo oxidation towards dimethoxybilipurpurins. The magnetic behaviour of Cu(II) etiobiliverdinate-IV-γ in the solid state shows an intramolecular weak antiferromagnetic coupling d9Cu-to-π-radical (J=−23 cm−1) and an intermolecular weak antiferromagnetic coupling π-radical-to-π-radical (J=−45 cm−1). The analogy of this magnetic behaviour to that of the π cation radical of metalloporphyrins is discussed.

On the chemistry of pyrrole pigments, XCVI: An efficient synthesis of corrphycenes

By means of copper catalyzed intramolecular coupling of the easily accessible 1,2-bis-(1-iodo-dipyrrin-9-yl)-ethanes and subsequent demetallation of the intermediate copper complexes corrphycenes could be prepared in nearly 40% overall yields.

On the chemistry of pyrrole pigments, XCVII: Synthesis, stereochemistry, and solvatochromic effects of a 1-(dipyrrinon-9-yl)-3-(dipyrrinon-9-ylidene)-1-propene

By condensing a dipyrrinon-9-yl-acrolein with a dipyrrinone unsubstituted in position 9, an unsymmetricb-vinylogous verdinoid pigment was prepared. The configuration of this molecule was elucidated by means of 2D1H NMR experiments to be (4Z,10E,12Z,17Z) in solutions of chloroform and dimethylsulfoxide, and its conformation was derived to be 5syn,9syn,11anti,16syn. The pronounced solvatochromic effect of this molecule with a cyclic helical geometry could be explained by solvent induced conformational changes.

Reactivity of pyrrole pigments, XX. On the structure of Cu(II) and Zn(II) tripyrrin-1-one chelates in solution

The Cu(II) and Zn(II) chelates of 12,14-dimethyl-2,3,7,8-tetraethyl-15H-tripyrrin-1-one, 12,13-dimethyl-2,3,7,8-tetraethyl-15H-tripyrrin-1-one, and their sulfonate derivatives are studied. The chelates show the expected structure of an NH dideprotonated ligand chelating the metal ion. However, in the case of the Zn chelate of 12,14-dimethyl-2,3,7,8-tetraethyl-15H-tripyrrin-1-one the ligand is only monodeprotonated, and the lactam ring is tautomerized to a hydroximino function.

Reactivity of pyrrole pigments, XIX. On the structure of Cu(II) and Zn(II) chelates of dipyrrins in solution

The Cu(II) and Zn(II) chelates of 1,2,3,7,9-pentamethyldipyrrin and 1,2,3,7,9-pentamethyl-8-sulfodipyrrin are studied. When metal acetates are used for the formation of the metal complexes, dipyrrinate metal acetates could be detected as precursors of thebis-dipyrrinates.

Inhibitory effect of hemin, chlorophyllin and related pyrrole pigments on the mutagenicity of benzo[ a]pyrene and its metabolites

Hemin and chlorophyllin are known to inhibit strongly the mutagenicity of benzo[ a]pyrene in the Salmonella assay. To further investigate this phenomenon, a series of these pyrrole pigments including pure samples of Cu- and Fe-chlorins were tested for their potency to inhibit the mutagenicity of benzo[ a]pyrene and its metabolites, benzo[ a]pyrene-7,8-diol, benzo[ a]pyrene4,5-epoxide, and benzo[ a]pyrene-7,8-diol-9,10-epoxide. Hemin was the most potent amongthe pigments tested for these inhibitions. Both hemin and Cu-chlorin accelerated efficiently the degradation of benzo[ a]pyrene-7,8-diol-9,10-epoxide, and this acceleration seemed to be the predominant mechanism by which these pigments inhibit the overall mutagenicity of benzo[ a]pyrene in Salmonella. Based on spectroscopic evidence, we speculate that a complex formation between hemin and benzo[ a]pyrene-7,8-diol-9,10-epoxide takes place and that this complexing is the cause of the accelerated degradation.

ChemInform Abstract: Reactivity of Pyrrole Pigments. Part 17. Reduction of Bile Pigments by Sodium Dithionite.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactivity of pyrrole pigments, part XVII. Reduction of bile pigments by sodium dithionite

Bilanediones can be easily obtained by sodium dithionite reduction of the corresponding alkyl-substituted bilindiones or biladiene-ac-diones. By reduction of vinyl-substituted dipyrrinones with sodium dithionite, the corresponding alkyl-substituted 4,5-dihydrodipyrrinones can be obtained.

Polymer bound pyrrole compounds, VIII. Water-soluble pyrrole pigments carrying polyether side chains

Mesoporphyrin IX and bilirubin IXα have been attached to one polyoxyethylene chain of molecular mass of about 2000. In the first case, one ester and one amide are prepared involving one of the two carboxylic acid groups of mesoporphyrin; in the second, the product is the thioether adduct to the exo-vinyl group of bilirubin. The products are in all cases water-soluble chromopolymers. Their absorption and emission spectra in water are discussed and interpreted in terms of aggregation.

Reactivity of pyrrole pigments: Part 16. Mesobiliverdin IXα and mesobilirubin IXα bridged between the propionic acid substituents

Mesobiliverdin IXα diesters of α,ω-dialkanols were obtained by reaction of mesobiliverdin IXα dicesium salt with diiodomethane, 1,3-dibromopropane and 1,4-dibromobutane. Mesobiliverdin IXα methylene diester was tested and compared to mesobiliverdin IXα dimethyl ester, for their photoisomerization behaviour, addition of nucleophiles at C10, protonation, and deprotonation. The constriction imposed by the internal cycle to the flexibility around the two central rings has no appreciable effect on these reactions. In fact, the small pK a differences in the protonation indicate that previous results, on the protonation of biliverdins bridged between the end rings, can be explained through a stretched structure of the protonated bile pigment implying a change in the configuration or conformation of one end ring.

On the chemistry of pyrrole pigments, XCI: Copper complexes of pyridinologous linear tri- and tetra-pyrroles as cyclopropanation catalysts

In addition to two recently described pyridinologous linear tri- and tetrapyrroles a biisoquinologous system was prepared and its geometrical features derived by means of NMR measurements and force field calculations. The copper complexes of these three ligands were isolated and characterized, and then used as catalysts in the cyclopropanation of styrene. The results were found to be similar to those reported for a variety of catalysts in literature. Thus, it was demonstrated that these systems can be used in principle as catalysts.

On the chemistry of pyrrole pigments, XC: Pyridinologous linear tri- and tetrapyrroles

One pyridinologous linear tripyrrole and two pyridinologous linear tetrapyrroles were prepared, and their structural aspects derived from spectroscopic measurements and force field calculations. The properties of these novel pyrrole pigments are compared with those of analogous linear tri- and tetrapyrroles.

Reactivity of pyrrole pigments, part 15: On the oxidation of bilirubins and biliverdins

Characteristic oxidation reactions of bilin-1,19-diones (biliverdins) and biladien-ac-1,19-diones (bilirubins) were reinvestigated. These include bromine and iodine oxidation of biliverdin IXα, bilirubin IXα and their Zn(II) complexes, the reaction described by Siedel (1941) of mesobilirubin XIIIα dimethyl ester with nitric acid (Gmelin reaction) and Smith's oxidation (1977) of etiobiliverdin IVγ using Tl triacetate and Pb tetra-acetate. For some of these reaction products new structures were assigned on the basis of their spectrometric data. These structures agreed with the expected reactivity pattern of biliverdins and bilirubins.

Reactivity of pyrrole pigments: Part 14. The electrochemical oxidation and reduction of bile pigments

The anodic oxidation of dipyrrin-1(10 H)-ones, biladiene- ac-diones (bilirubins), bilindiones (biliverdins), two 2,3-dihydrobilindiones and phycocyanobilin dimethyl ester were studied by cyclic voltammetry in N,N-dimethylformamide. The cathodic reduction of the bilindiones, the 2,3-dihydrobilindiones and phycocyanobilin dimethyl ester was also studied by voltammetry and polarography. Substituent effects and the influence of bases on the oxidative behaviour of these compounds were studied. The results are discussed in relation to the biological role of bile pigments. Phycocyanobilin dimethyl ester shows a clearly different oxidative behaviour with respect to the bile pigments tested.

ChemInform Abstract: Reactivity of Pyrrole Pigments. Part 13. Identification of the Reaction Product Generated from Bile Pigments by the Superoxide Anion.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

On the chemistry of pyrrole pigments, LXXXVII: The apomyoglobin heme pocket as a reaction vessel in bile pigment chemistry

An apomyoglobin biliverdin complex was reduced to a bilirubin apomyoglobin complex with retention of the helix chirality of the chromophore. Chelation of the mesobiliverdin-XIIIα apomyoglobin complex with zinc ions in aqueous solution yielded an enantiomer of the corresponding derivative. These two systems document the possibility of using the heme pocket of apomyoglobin to execute stereospecific reactions. The chiroptical properties of the two product systems are discussed.

Reactivity of pyrrole pigments, part 13: Identification of the reaction product generated from bile pigments by the superoxide anion

The UV/Vis spectra of the conjugated bases (NH deprotonation) of biliverdin IX α (BV), mesobiliverdin IX α (MBV), biliverdin IX α dimethyl ester (BV -DME) and mesobiliverdin IX α dimethyl ester (MBV - DME) are shown. They resemble those obtained for the reaction products of these biliverdins with superoxide anion ( $$o_2^{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{ - } } $$ ). These results confirm that the bile pigments react with $$o_2^{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{ - } } $$ giving the lactam NH deprotonated conjugated bases and inducing $$o_2^{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{ - } } $$ dismutation. The spectrometric titrations ofBV, MBV and their dimehyl esters show that the lactam NH of the vinyl substituted biliverdins is more acidic (ΔpK a ℞0.5). The spectra of the lactam NH bisdeprotonated conjugated bases of the bilatrienes-abc studied (BV 4− andMBV 4−) can be obtained inDMSO/H2O/OH− systems of high basicity function (H−℞23). Because of the low oxidation potentials ofBV 3− and of the corresponding trianion of bilirubin IX α (studied by voltammetry) an alternative metabolic degradative pathway is suggested for bilirubin, involving the interaction in lipophilic media with $$o_2^{\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdot}$}}{ - } } $$ and oxidation of the conjugated base generated by NH deprotonation.

Synthesic applications of the bromomethyl-Nbb resin. Esters of a model for the natural pyrrole pigments by transesterification of their ortho-nitrobenzyl ester polystyrene supported precursors

Synthesic applications of the bromomethyl-Nbb resin. Esters of a model for the natural pyrrole pigments by transesterification of their ortho-nitrobenzyl ester polystyrene supported precursors

ChemInform Abstract: Pyrrole Pigments. Part 76. Synthesis of Symmetrically Substituted 2,2′‐Bipyrroles by Oxidative Coupling.

ChemInform Abstract: Pyrrole Pigments. Part 76. Synthesis of Symmetrically Substituted 2,2′‐Bipyrroles by Oxidative Coupling.