Ion-molecular interactions in the metalloporphyrin-acid system in liquid solutions

Ломова, Т. Н.; Klyueva, M. E.; Mozhzhukhina, E. G.; Tyulyaeva, E. Yu.; Бичан, Н. Г.; Зайцева, С. В.; Зданович, С. А.

doi:10.1134/s0022476614010314

Cited by 6 publications

(10 citation statements)

References 15 publications

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“…In glacial acetic acid, Ir(III) complexes form molecular solutions without proton transfer [24]. The spectrum of (Cl)(H 2 O)IrTPP is similar to the UV vis spectrum in chloroform but contains bathochromi cally shifted by ~10 nm Q bands (Fig.…”

Section: Resultsmentioning

confidence: 87%

Chemical structure and reactions of axially coordinated iridium(III) porphyrins

Tyulyaeva

Mozhzhukhina

Бичан

et al. 2015

Russ. J. Inorg. Chem.

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Variable valence in chemical compounds is one of the reasons of structure variety of iridium coordination compounds, in particular, complexes with tetrapyrrole ligands. Few Ir(I) porphyrin complexes are presented in the literature by several works. Among described compounds are intermediate [Ir I (CO) 3 ] 2 OEP in the course of (Cl)(CO)Ir III OEP synthesis from [Ir(cod)Cl] 2 (cod is cyclooctadiene) and H 2 OEP [1], tetracoordinated bis[iridium(I)] complex with N confused porphyrin (NCTPP) (CO) 4 (NCTPP is the dianion of N confused 5,10,15,20 tetraphenyl 21H,23H porphine) [2], and donor acceptor SAT (sitting a top) complex μ (5,10,15,20 tetraphenylpor phine) bis chloroiridium(I) [3]. Oxidation state 3+ and CN = 6 are more typical for iridium [4]. Struc tures with central Ir(III) atom were studied for com pounds of classes hexaphyrins [5], corroles [6, 7], por phyrins [8-11], and N confused porphyrins [2].According to [5][6][7][8][9][10][11], Ir(III) porphyrinoids display catalytic and redox activity, which depends on the state of axial coordination sites on the metal atom. Porphyrin complexes show distinct photoluminescent properties [12,13]. There is a rapidly growing interest in the chemistry of aromatic macroheterocyclic irid ium compounds in recent years due to the noted fea tures.The aim of this work is to study the state and reac tions of 5,10,15,20 tetraphenyl 21H,23H porphine (H 2 TPP) complexes with trivalent iridium cation (for 2 I Ir mula) in protolytic solvents AcOH and CF 3 COOH and to reveal the effect of modification at the fifth and sixth axial coordination sites in molecule on the phys icochemical properties and reactivity of the com plexes. We also obtained data for similar Re 3+ complexes presented for comparison. Only few works in the litera ture were dedicated to the physical chemistry of Re 3+ complexes with tetrapyrrole ligands: for derivatives of trans difluorophthalocyanine trans [Re(F) 2 pc 2-]and N confused porphyrin Re III (NFP)OL (P = TPP 2-) [14,15]. [16]. A mixture of H 2 TPP (0.00360 g), (Н 3 O) 2 IrCl 6 (0.01115 g) (molar ratio 1 : 5), and phenol (2.0 g) was heated under reflux for 3 h. Reaction completion was detected by the dis appearance of Н 2 ТРР in the reaction mixture using thin layer chromatography (TLC) (Silufol, chloro form). The reaction mixture was cooled, dissolved in chloroform, and washed many times with warm dis tilled water in a separating funnel to remove phenol. The chloroform solution was concentrated and chro matographed on Brockmann activity grade II alumina using chloroform as an eluent. There were three zones. The substances of the first and the third zones were purified repeatedly. Trace amounts of compound of unknown composition from the second zone were dis carded. EXPERIMENTAL (5,10,15,20 tetraphenylporphinato)chloroaquairi dium(III) (Cl)(H 2 O)Ir III TPPAbstract-Effect of modification of the axial (fifth and sixth) coordination sites on the physicochemical properties and reactivity of iridium(III) complexes with 5,10,15,20 tetraphenyl 21H,23H porphine ...

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Section: Resultsmentioning

confidence: 87%

Chemical structure and reactions of axially coordinated iridium(III) porphyrins

Tyulyaeva

Mozhzhukhina

Бичан

et al. 2015

Russ. J. Inorg. Chem.

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“…The product of the interaction MP with proton is easy identified due to an unique UV-vis absorption spectrum (Figure 1, line 3) with the bands near 440-450 nm, 540 nm, and 700 nm, which weakly depend on the central atom and noticeably change when the chromophore is functionally substituted. [90] The bands near 540 nm shifts to short waves in most cases in comparison with the corresponding spectrum in CHCl 3 . The bands near 440-450 nm and 700 nm undergo a hypsochromic shift when the concentration of strong acid is decreased.…”

Section: Macrocycle Protonation Reactionsmentioning

confidence: 83%

“…The scheme of redox reactions occurring during the complex formation involving Pb 2+ as the reducing agent was suggested. [33] Properties and Application of p-Metal Porphyrins…”

Section: The Redox Processes During the Synthesis Of The Lead Porphyr...mentioning

confidence: 99%

“…[6] An unprecedented type of UV-vis absorption spectrum, which combined stable main group porphyrin complexes with transition d-metal complexes by its uni-formity, was discovered for the first time in the work [88] and received further interpretation. [89,90] That is discussed in the next section in the context of the chemical reactivity towards acids.…”

Section: Uv-vis Absorption Spectra Of Main Group Porphyrin Complexesmentioning

confidence: 99%

“…[31,32] The second exception is Pb, the complexes of which demonstrate the composition of MP without axial anionic ligands as well as the ones of X 2 PbP (X is monoanion). [33,34] Bi(por)(X) (por is TPP or 5,10,15,20-tetra-p-chlorophenylporphine, X is NO 3 , Cl, Br, or I) formed by the central ion in the low oxidation state (+3) crystallize as doubly bridged through Cl or Br centrosymmetric dimers. [35] Unusual coordination geometries are the characteristic properties for porphyrin complexes of the period 6 main group elements.…”

Section: Introductionmentioning

confidence: 99%

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The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

Ломова¹

2021

MHC

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The article is the short review of the recent works in the physical and applied chemistry of the main group porphyrin complexes. Several classic articles on the topic are included in the discussion. Special attention is paid to the specificity of preparation methods, with the demonstration of the specific original syntheses, as well as of optical properties, reactivity and new applications. The prospects of the main group porphyrin complexes in medicine, catalysis, and optoelectronics are briefly presented.

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