Electrochemical and spectroscopic studies of poly(diethoxyphosphoryl)porphyrins

Abstract The synthesis and electrochemical characterization of two related series of porphyrins bearing diethoxyphosphoryl groups are reported. One group of compounds is represented as (T( p -R)PP)M where R = phos = P(O)(OEt) 2 and M = Zn(II) or H 2 while the other is represented as (di( p -R)Pdi(phos)P)M where R = P(O)(OEt) 2 , H or CH 3 and M = Zn(II) or H 2 . Each porphyrin was investigated by electrochemistry and thin-layer spectroelectrochemistry in CH 2 Cl 2 , CDCl 3 , CHCl 3 or PhCN containing tetra- n -butylammonium perchlorate (TBAP) as supporting electrolyte. The highly electron-withdrawing P(O)(OEt) 2 groups lead to easier reductions and harder oxidations than the two comparison …

Clarification of the oxidation state of cobalt corroles inheterogeneous and homogeneous catalytic reduction of dioxygen

Co(III) corroles were investigated as efficient catalysts for the reduction of dioxygen in the presence of perchloric acid in both heterogeneous and homogeneous systems. The investigated compounds are (5,10,15-tris(pentafluorophenyl)corrole)cobalt (TPFCor)Co, (10-pentafluorophenyl-5,15-dimesitylcorrole)cobalt (F 5PhMes 2Cor)Co, and (5,10,15-trismesitylcorrole)cobalt (Mes 3Cor)Co, all of which contain bulky substituents at the three meso positions of the corrole macrocycle. Cyclic voltammetry and rotating ring-disk electrode voltammetry were used to examine the catalytic activity of the compounds when adsorbed on the surface of a graphite electrode in the presence of 1.0 M perchloric acid, a…

Synthesis, Characterization, and X-ray Crystal Structures of Cyclam Derivatives. 5. Copper(II) Binding Studies of a Pyridine-Strapped 5,12-Dioxocyclam-Based Macrobicycle1

The copper(II) binding properties of the macrobicyclic diamide 1,9,12,18,22-pentaazatricyclo[7.6.6.1(3,7)]docosa-3,5,7(22)-triene-13,19-dione (L1) have been fully investigated by spectroscopic (IR, UV-vis, EPR, MALDI-TOF MS), X-ray diffraction, potentiometric, electrochemical, and spectroelectrochemical methods. This constrained receptor possesses a hemispherical cavity created by cross-bridging the 1 and 8 positions of trans-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,12-dione, L2) with a 2,6-pyridyl strap. Treatment of L1 with a copper salt in methanol produces a red complex of [Cu(L1H(-1))]+ formula in which the copper atom is embedded in a 13-membered ring and coordinated by both a…

Base Control of Electron-Transfer Reactions of Manganese(III) Porphyrins

Homogeneous electron-transfer kinetics for the reduction of four different manganese(III) porphyrins using different reductants were examined in deaerated acetonitrile, and the resulting data were evaluated in light of the Marcus theory of electron transfer to determine electron-exchange rate constants between manganese(III) and manganese(II) porphyrins. The investigated compounds are represented as (P)MnCl, where P = the dianion of dodecaphenylporphyrin (DPPX; X = H20, Cl12H8, or F20) or tetraphenylporphyrin (TPP). The electron transfer from semiquinone radical anion derivatives to (P)MnIIICl leads to formation of the corresponding MnII complex, [(P)MnIICl]−. The electron-exchange rate con…

Metallomacrocycles with metalmetal bonds: synthesis, characterization and electrochemistry of [(P)SnRe(CO)5]BF4 and [{(P)Sn}2Re(CO)4]BF4 derivatives, where P = tetra-p-tolyporphyrin or tetra-m-tolylporphyrin

Abstract The synthesis and characterization of bimetallic and trimetallic porphyrins of the type [(P)SnRe(CO) 5 ]BF 4 and [{(P)Sn} 2 Re(CO) 4 ]BF 4 are reported where P is the dianion of tetra- p -tolyporphyrin (TpTP) or tetra- m -tolyporphyrin (TmTP). These metal-metal bonded complexes were synthesized by reaction of Re 2 (CO) 10 with the corresponding (P)SnCl 2 derivatives in 1,2-dichlorobenzene followed by a reaction with NaBF 4 or TBABF 4 in toluene to give the BF − 4 salt. Each compound was characterized by a variety of spectroscopic and electrochemical techniques while the structures were assigned on the basis of FAB mass spectral data and by comparison of their physicochemical proper…

Corroles with Group 15 Ions. 2. Synthesis and Characterization of Octaethylcorroles Containing a Phosphorus Central Atom

The synthesis, spectroscopic characterization, and electrochemistry of five new phosphorus corroles are reported. The investigated complexes contain alkyl, aryl, oxo, or hydrido axial ligands and are represented as (OEC)P(H)2, (OEC)P(CH3)2, (OEC)P(C6H5)2, (OEC)P=O, and [(OEC)P(CH3)]+ClO4-, where OEC is the trianion of octaethylcorrole. The products of electrooxidation and/or electroreduction were also characterized by UV-vis and ESR spectroscopy. Correlations are shown to exist between reversible half-wave potentials for the first oxidation and first reduction of each compound and the combined electronegativity of the central ion and the axial ligand(s). The electrochemical HOMO-LUMO gap, d…

New Developments in Corrole Chemistry: Special Emphasis on Face-to-Face Bismacrocycles

Electrochemical and Spectroelectrochemical Properties of Free-Base Pyridyl- and N -Alkyl-4-Pyridylporphyrins in Nonaqueous Media

International audience; Twelve structurally related pyridyl and meso-N-methylpyridylporphyrin derivatives are investigated electrochemically in different nonaqueous media. The UV/Vis spectrum of each newly investigated porphyrin was measured before and after electro-reduction and, based on this data, the site of electron transfer is proposed. An interaction occurs between the meso-pyridyl or meso-N-alkyl-4-pyridyl substituents and the porphyrin p-ring system, the magnitude of which depends upon the number of linked pyridyl or N-alkyl-4-pyridyl groups in the compound, the solvent, the supporting electrolyte, and/or other anions added to the solution.

ChemInform Abstract: Synthesis, Electrochemistry, and Spectroelectrochemistry of (P)Ge(Fc)2 and (P)Ge(C6H5)(Fc): First Example of Metal-Carbon-σ-Bonded Porphyrins with Two Different Axial Groups.

Electrochemistry and spectroelectrochemistry of bismanganese biscorroles dyads

Three manganese biscorrole dyads were synthesized, physicochemically characterized and investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous media. Each dyad contained the same two corroles linked in a face-to-face arrangement via one of the three different linking groups, 9,9-dimethylxanthene, anthracene or diphenylether, the exact nature of which determined the distance and possible interaction between the two metallomacrocycles. The initial compounds contained Mn ( III ) in their air stable form and were shown to exhibit two major redox processes, one being a Mn (III)/ Mn (IV) conversion and the other being either Mn ( III )/ Mn ( II ) or reduction at the c…

Alkyl and Aryl Substituted Corroles. 2. Synthesis and Characterization of Linked “Face-to-Face” Biscorroles. X-ray Structure of (BCA)Co2(py)3, Where BCA Represents a Biscorrole with an Anthracenyl Bridge

The synthesis, spectroscopic properties, and electrochemistry of (BCA)Co(2) and (BCB)Co(2) are described where BCA and BCB represent biscorroles linked by an anthracenyl (A) or a biphenylenyl (B) bridge. The pyridine and CO binding properties of (BCA)Co(2) and (BCB)Co(2) are also presented, and one of the compounds in its pyridine-ligated form, (BCA)Co(2)(py)(3), is structurally characterized. The data on the biscorroles are compared on one hand to the monocorrole having the same substitution pattern and on the other hand to bisporphyrins having two Co(II) ions and the same anthracenyl or biphenylenyl linkers in order to better understand the interaction which occurs between the two corrole…

Synthesis of an anthracenyl bridged porphyrin–corrole bismacrocycle. Physicochemical and electrochemical characterisation of the biscobalt μ-superoxo derivative

Abstract Dicobalt or heterobimetallic cofacial bisporphyrins are up till now amongst the very few molecular electrocatalysts able to promote the direct reduction of dioxygen to water via a four-electron process in acidic medium. Numerous studies have been devoted to elucidate the key steps of this catalytic reaction and an important result has revealed an unexpected high dioxygen affinity for a mixed valence Co(II)/Co(III) cofacial porphyrin, the key intermediate complex being a μ-superoxo derivative. At the same time, the great importance assumed by ‘Pacman’ porphyrins and the recent developments in corrole chemistry have provided the stimulation to synthesise porphyrin–corrole dyads which…

Synthesis, Characterization, and Electrochemistry of Open-Chain Pentapyrroles and Sapphyrins with Highly Electron-Withdrawing meso -Tetraaryl Substituents

International audience; A series of open-chain pentapyrroles and sapphyrins with highly electron-withdrawing substituents (i.e., CN, CF3 , or CO2 Me) on the meso-phenyl rings was synthesized and characterized as to the spectral properties, protonation reactions, and electrochemistry in non-aqueous media. The investigated compounds are represented as (Ar)4 PPyH3 and (Ar)4 SapH3 where PPy and Sap correspond to the tri-anion of the open-chain pentapyrrole and sapphyrin, respectively, and Ar=p-CNPh, p-CF3 Ph, or p-CO2 MePh. UV/Vis and 1 H NMR spectroscopy as well as mass spectrometry data are given for the confirmation of the structures for the newly synthesized compounds. An X-ray structure fo…

The Difficult Marriage of Triarylcorroles with Zinc and Nickel Ions.

The coordination chemistry of corrole has witnessed a great improvement in the past few years and its Periodic Table has been widened to be so large that it is compared with that of porphyrins. However, Ni and Zn ions, commonly used with porphyrins for both synthetic and theoretical purposes, are sparsely reported in the case of corroles. Here, we report synthetic protocols for preparing Ni and Zn triarylcorrole complexes. In the case of Zn, the preliminary oxidation of the free base corrole in DMSO to the neutral corrole radical is a necessary step to obtain the coordination of the metal ion, because the direct reaction led to the formation of an open-chain tetrapyrrole. The Ni complex cou…

Alkyl- and aryl-substituted corroles. 4. Solvent effects on the electrochemical and spectral properties of cobalt corroles.

Solvent effects on the electrochemistry and spectroscopic properties of alkyl- and aryl-substituted corroles in nonaqueous media are reported. The oxidation and reduction of six compounds containing zero to seven phenyl or substituted phenyl groups on the macrocycle were studied in four different nonaqueous solvents (CH(2)Cl(2), PhCN, THF, and pyridine) containing 0.1 M tetra-n-butylammonium perchlorate. Dimers were formed upon oxidation of all corroles in CH(2)Cl(2), but this was not the case in the other three solvents, where either monomers or dimers were formed upon oxidation depending upon the solvent Gutmann donor number and the number or location of aryl substituents on the macrocycl…

Alkyl- and aryl-substituted corroles. 5. Synthesis, physicochemical properties, and X-ray structural characterization of copper biscorroles and porphyrin-corrole dyads.

The synthesis and characterization of cofacial copper biscorroles and porphyrin-corroles linked by a biphenylenyl or anthracenyl spacer are described. The investigated compounds are represented as (BCA)Cu(2) and (BCB)Cu(2) in the case of the biscorrole (BC) derivatives and (PCA)Cu(2) and (PCB)Cu(2) in the case of porphyrin (P)-corrole (C) dyads, where A and B represent the anthracenyl and biphenylenyl bridges, respectively. A related monomeric corrole (Me(4)Ph(5)Cor)Cu and monomeric porphyrin (Me(2)Et(6)PhP)Cu that comprise the two halves of the porphyrin-corrole dyads were also studied. Electron spin resonance (ESR), (1)H NMR, and magnetic measurements data demonstrate that the copper corr…

Metalloporphyrins with metalmetal σ-bonds. Synthesis, spectroscopic characterization, and electrochemistry of (P)MRe(CO)5 where P is the dianion of octaethylphorphyrin (OEP) or tetraphenylporphyrin (TPP) and M = Al, Ga, In or Tl

Abstract The synthesis, physicochemical properties, and electrochemistry of a new series of metal metal σ-bonded metalloporphyrins are reported. The investigated compounds are represented as (P)MRe(CO)5 where P is the dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP) and M = Al, Ga, In, or Tl. These compounds provide the first examples of Al and Ga metalloporphyrins with covalent metalmetal bonds as well as give the first series of compounds in which the same metalate anion is covalently bonded to four different group 13 metalloporphyrins. Each synthesized complex was characterized by 1H NMR, IR, and UV-visible spectroscopy as well as by electrochemistry. Graham Δσ and Δπ …

Electrochemical and spectroscopic characterization of cobalt and zinc diaza‐18‐crown‐6 porphyrins and of a zinc dioxocyclam porphyrin

The synthesis and electrochemical characterization of ‘crowned’ and ‘dioxocyclam’ metalloporphyrins containing Co(II) or Zn(II) metal ions is presented. Each complex is also characterized by mass spectrometry in addition to a variety of spectroscopic techniques (UV-vis, FTIR, ESR (in the case of Co(II)) and 1H and 13CNMR spectroscopy).

Electrochemistry and spectroelectrochemistry of heterobimetallic porphyrin-corrole dyads. Influence of the spacer, metal ion, and oxidation state on the pyridine binding ability.

Combined electrochemical and UV-visible spectroelectrochemical methods were utilized to elucidate the prevailing mechanisms for electroreduction of previously synthesized porphyrin-corrole dyads of the form (PCY)H2Co and (PCY)MClCoCl where M = Fe(III) or Mn(III), PC = porphyrin-corrole, and Y is a bridging group, either biphenylenyl (B), 9,9-dimethylxanthenyl (X), anthracenyl (A), or dibenzofuranyl (O). These studies were carried out in pyridine, conditions under which the cobalt(IV) corrole in (PCY)MClCoCl is immediately reduced to its Co(III) form, thus enabling direct comparisons with the free-base porphyrin dyad, (PCY)H2Co(III) under the same solution conditions. The compounds are all r…

Synthesis, electrochemistry, protonation and X-ray analysis of meso-aryl substituted open-chain pentapyrroles

Five meso-tetraaryl open-chain pentapyrroles were synthesized and characterized as to their electrochemistry and protonation reactions in nonaqueous media. The investigated compounds are represented as (Ar)4PPyH3 where Ar [Formula: see text],[Formula: see text]-F2Ph, [Formula: see text]-BrPh, Ph, [Formula: see text],[Formula: see text],[Formula: see text]-(OMe)3Ph or [Formula: see text]-MePh and were characterized by UV-vis and 1H NMR spectroscopy, mass spectrometry and electrochemistry. Cyclic voltammetry was used to measure redox potentials, while protonation involving the conversion of (Ar)4PPyH3 to [(Ar)4PPyH5][Formula: see text] was monitored by UV-vis absorption spectroscopy. Equilib…

Non-linear optical, electrochemical and spectroelectrochemical properties of amphiphilic inner salt porphyrinic systems

Three zwitterionic meso-substituted A3B- and AB2C-porphyrins containing one sulfonato alkylpyridinium substituent and three or two alkoxy-substituted phenyl groups were synthesized in good yield and fully characterized as to their physicochemical properties by a variety of techniques. This new series of inner salt donor-acceptor meso-substituted porphyrin derivatives were prepared for possible application as amphiphilic probes for membrane insertion in the area of combined second-harmonic and two-photon fluorescence cellular microscopy. To this end, the linear and nonlinear optical properties of the compounds were characterized, together with their electrochemical and spectroelectrochemica…

Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortion of the Macrocycle

Slow electron transfer to manganese(iii) porphyrins results when the macrocycle deviates from planarity. This was demonstrated by measuring the kinetics of homogeneous electron transfer from a series of semiquinone radical anions to synthetic manganese porphyrins (shown schematically; R1 =H, Cl, F; R2 =H, F). Three of the four porphyrins studied have nonplanar macrocycles. These results could have implications for the role of manganese in biological electron transfer processes.

Tuning the Electrochemistry of Free-Base Porphyrins in Acidic Nonaqueous Media: Influence of Solvent, Supporting Electrolyte, and Ring Substituents

International audience; A detailed study of reduction potentials, electroreduction mechanisms and acid-base chemistry was carried out on two series of free-base porphyrins in nonaqueous media. The first series is represented by four-pyrrole substituted tetraphenylporphyrin (TPP) derivatives, two of which are planar and two of which are nonplanar in their non-protonated form. The second comprises porphyrins with 0-4 meso-phenyl groups on the macrocycle. Equilibrium constants for conversion of each neutral porphyrin to its diprotic [H4P] 2+ form were determined and the electrochemistry was then elucidated as a function of: (i) type of nonaqueous solvent, (ii) anion of supporting electrolyte, …

Effect of Peripheral Substitution and Extended Conjugation on the Redox Potentials of Nickel Porphycenes

Eight different nickel porphycenes bearing substituents on the pyrrole β and/or ethylenic carbon positions of the macrocycle were investigated as to their redox properties in benzonitrile containin...

Synthesis, physicochemical and electrochemical properties of metal–metal bonded ruthenium corrole homodimers

Abstract Two diruthenium(III,III) corrole dimers, [(Et 6 Me 2 Cor)Ru] 2 and [(Me 6 Et 2 Cor)Ru] 2 , where Et 6 Me 2 Cor and Me 6 Et 2 Cor are the 2,3,8,12,17,18-hexaethyl-7,13-dimethylcorrole and 8,12-diethyl-2,3,7,13,17,18-hexamethylcorrole trianions, respectively, were synthesized and characterized as to their spectroscopic and electrochemical properties. They exhibit up to three oxidations and two reductions by cyclic voltammetry in CH 2 Cl 2 or pyridine containing 0.1 M TBAP, almost all of which are electrochemically reversible on the voltammetric and/or thin-layer spectroelectrochemical timescale. The two reductions and the first two oxidations involve one-electron transfer processes w…

Solvent, anion and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles

A series of manganese(III) corroles were investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous solvents. Up to three oxidations and one reduction were obtained for each complex depending on the solvents. The main compound discussed in this paper is the meso-substituted manganese corrole, (Mes 2PhCor)Mn, and the main points are how changes in axially coordinated anion and solvent will affect the redox potentials and UV-vis spectra of each electrogenerated species in oxidation states of Mn(III), Mn(IV), or Mn(II). The anions OAc (-), Cl (-), CN (-), and SCN (-) were found to form five-coordinate complexes with the neutral Mn(III) corrole while two OH (-) or F (-)…

Inside Cover: Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers (Chem. Eur. J. 34/2015)

Coordination self-assembly through weak interactions in meso-dialkoxyphosphoryl-substituted zinc porphyrinates.

International audience; The self-assembly of seven zinc 10-(dialkoxyphosphoryl)-5,15-diarylporphyrinates Zn5-Zn11 containing different substituents at the phosphonate and aryl groups was investigated. Single crystals of Zn5-Zn9 complexes were grown under the same conditions and analyzed by X-ray structural analysis. A supramolecular self-assembly is observed in all crystals through weak coordinative bonding of the phosphoryl group of one porphyrin molecule to the zinc(II) ion of a second porphyrin molecule. The geometry of the porphyrin macrocycle is similar in all of the studied crystals and the central zinc atom in each case adopts a distorted tetragonal pyramidal environment. However, th…

Effect of axially bound anions on the electroreduction of tin(IV) porphyrins in tetrahydrofuran

The spectroscopic characterization and electrochemistry of SnL(X)2 is presented where L is the dianion of tetra-p-tolylporphyrin or tetra-m-tolylporphyrin and X is ClO4–, Br–, Cl–, F–, or OH–. In all cases, electroreduction leads to porphyrin π anion radicals and dianions which were characterized in tetrahydrofuran by spectroelectrochemistry and e.s.r. spectroscopy. Dissociation of one ClO4– ion from SnL(ClO4)2 occurs before electroreduction of the complex but no dissociation is observed either before or after electroreduction of SnL(F)2 or SnL(OH)2. In contrast, one Br– ion dissociates after the first electron addition to SnL(Br)2 while one Cl– ion dissociates from SnL(Cl)2 after the secon…

Alkyl and aryl substituted corroles. 3. Reactions of cofacial cobalt biscorroles and porphyrin-corroles with pyridine and carbon monoxide.

The synthesis and characterization of three new cofacial biscorroles and three new linked Co(II) porphyrins and Co(III) corroles with the same face to face orientation are described. The biscorroles are represented as (BCS)Co(2), (BCO)Co(2), (BCX)Co(2) while the porphyrin-corrole dyads are represented as (PCA)Co(2), (PCB)Co(2), (PCO)Co(2) where BC represents the Co(III) cofacial biscorroles and PC represents the porphyrin-corrole complexes which are linked to each other by a dibenzothiophene (S), dibenzofuran (O), or 9,9-dimethylxanthene (X) bridge in the case of the corroles and an anthracene (A), biphenylene (B), or dibenzofuran (O) bridge in the case of the mixed macrocycle derivatives. …

Tetracationic and Tetraanionic Manganese Porphyrins: Electrochemical and Spectroelectrochemical Characterization

International audience; The electrochemistry and spectroelectrochemistry of four tetrapositively charged and two tetranegatively charged porphyrins were characterized in two nonaqueous solvents (dimethyl sulfoxide and N,N-dimethylformamide) containing 0.1 M tetra-n-butylammonium perchlorate. The tetrapositively charged compounds are represented by the tetrapyridylporphyrins [TRPyPM]4+(X-)4, where R is a methyl or [2-[2-(2-methoxy)ethoxy]ethoxy]ethyl group, M = MnIIII, MnIIICl, CuII, or PdII, and X = I- or Cl-. The tetranegatively charged porphyrins are represented by the tetrasulfonato derivatives [TPPSMn(OAc)]4-(NH4+)4 and [TArPSMn(OAc)]4-(NH4+)4, where Ar = 4-O-[2-[2-(2-methoxy)ethoxy]eth…

Protonation and Electrochemical Properties of Pyridyl- and Sulfonatophenyl-Substituted Porphyrins in Nonaqueous Media

International audience; The protonation and electrochemical properties of positively charged and negatively charged porphyrins are reported in up to five different nonaqueous solvents. The positively charged porphyrins are represented by mono- and di-pyridyl derivatives having the formula Pyx(PhMe)4-xPM, where P=the dianion of the porphyrin macrocycle, PhMe is a meso-tolyl group, Py a meso-pyridyl group, x=1 or 2, and M=H2, NiII, CuII, ZnII, or CoII. The negatively charged porphyrins are comprised of meso-tetrasulfonato derivatives having the formula [(R)4(TPPS)H2]4−(X+)4, where [(TPPS)H2]4− represents the porphyrin with four SO3− groups on the meso-phenyl substituents of the macrocycle, R=…

ChemInform Abstract: Synthesis and Electrode Reactions of Difluorogermanium(IV) Porphyrins. Molecular Stereochemistry and Crystal Structure of Difluoro-(2,3,7,8,12,13,17,18-octaethylporphyrinato)germanium(IV).

The difluorogermanium(IV) porphyrins [GeF2(P)][P = 2,3,7,8,12,13,17,18-octaethylporphyrinate(2–)(oep), 5,10,15,20-tetraphenylporphyrinate(2–)(tpp), or 5,10,15,20-tetra-p-tolylporphyrinate(2–)(tptp)] have been prepared by reacting hydrogen fluoride with the appropriate dichloro derivative [GeCl2(P)]. The complexes were characterized by elemental analysis, 1H n.m.r., i.r., and u.v.–visible spectroscopy. The electrochemical behaviour was investigated in non-aqueous media while spectroelectrochemistry and e.s.r. were used to characterize the oxidized and reduced complexes. Each complex could be reversibly oxidized or reduced by one electron. In each case these electron additions or abstractions…

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

International audience; A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central c…

Electrochemistry and Spectroelectrochemistry of Bismanganese Porphyrin-Corrole Dyads

A series of homobimetallic manganese cofacial porphyrin-corrole dyads were synthesized and investigated as to their electrochemistry, spectroelectrochemistry, and ligand binding properties in nonaqueous media. Four dyads were investigated, each of which contained a Mn(III) corrole linked in a face-to-face arrangement with a Mn(III) porphyrin. The main difference between compounds in the series is the type of spacer, 9,9-dimethylxanthene, anthracene, dibenzofuran, or diphenylether, which determines the distance and interaction between the metallomacrocycles. Each redox process of the porphyrin-corrole dyads was assigned on the basis of spectroscopic and electrochemical data and by comparison…

Synthesis and reactivity of .sigma.-bonded silicon metalloporphyrins. Spectroscopic characterization and electrochemistry of (P)Si(R)2, (P)Si(R)X, and (P)SiX2, where R = C6H5 or CH3 and X = OH- or ClO4-

Mono-DMSO ligated cobalt nitrophenylcorroles: electrochemical and spectral characterization

Four mono-DMSO ligated cobalt corroles with one or three meso-nitrophenyl substituents on the macrocycle were synthesized and investigated as to their electrochemical and spectroscopic properties in CH2Cl2 and DMSO. Comparisons are made between redox reactions of the five-coordinate DMSO adducts in the current study and earlier examined five- and six-coordinate cobalt corroles with pyridine axial ligands which were characterized in a variety of nonaqueous electrochemical solvents. The binding of carbon monoxide (CO) is also investigated.

Catalytic activity of biscobalt porphyrin-corrole dyads toward the reduction of dioxygen

A series of biscobalt cofacial porphyrin-corrole dyads bearing mesityl substituents at the meso positions of the corrole ring were investigated as to their electrochemistry, spectroelectrochemistry, and CO binding properties in nonaqueous media and then applied to the surface of a graphite electrode and tested as electrocatalysts for the reduction of dioxygen to water or hydrogen peroxide in air-saturated aqueous solutions containing 1 M HClO(4). The catalytic reduction of O(2) with the same dyads was also investigated in the homogeneous phase using 1,1'-dimethylferrocene as a reductant in PhCN containing HClO(4). The examined compounds are represented as (PMes(2)CY)Co(2), where P = a porph…

Electrochemistry, spectroelectrochemistry and catalytic activity of biscobalt bisporphyrin dyads towards dioxygen reduction

Three face-to-face biscobalt bisporphyrin dyads, including one incorporating a copper(II) ion inside the linker, were synthesized and characterized both spectroscopically and electrochemically in three non-aqueous solvents, dichloromethane, benzonitrile and pyridine. The electrocatalytic reduction of dioxygen with these derivatives on an electrode surface in 1.0 M HClO4 was also investigated and the results are compared to that obtained with "regular" Pacman biscobalt bisporphyrins under the same experimental conditions. Surprisingly, the tris-metal species ( Cu-bisCo ) catalyzes the reduction of O2 mainly via a 2e- transfer process, leading to H2O2 , while the bis-metal (bisCo) catalyst p…

Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers

Herein the synthesis, spectroscopic characterization, two-photon absorption and electrochemical properties of 3,6-disubstituted carbazole tweezers is reported. A dimer resulting from a Glaser homocoupling was isolated during a Sonogashira coupling reaction between a diethynyl-carbazole spacer and a 5-bromo-triarylporphyrin and the properties of this original compound were compared with the 3,6-disubstituted carbazole bisporphyrin tweezers. The dyads reported herein present a two-photon absorption maximum at 920 nm with two-photon absorption cross-section in the 1200 GM range. Despite a strong linear absorption in the Soret region and moderate fluorescence quantum yield, they both lead to a …

Heterobimetallic complexes of cobalt(IV) porphyrin-corrole dyads. Synthesis, physicochemical properties, and X-ray structural characterization.

The synthesis of a novel family of heterobinuclear cofacial biphenylene (B), anthracene (A), 9,9-dimethylxanthene (X), or dibenzofuran (O) bridged porphyrin-corrole complexes, (PCY)MClCoCl, is reported, M being either an iron(III) or manganese(III) ion. Each complex was characterized by electrochemistry, mass spectrometry, UV-vis, IR, and electron spin resonance spectroscopy. Unlike previously examined biscobalt porphyrin-corrole dyads, the cobalt ion of the corrole moiety is present in a high-valence +4 oxidation state, as proven by electrochemistry, spectroelectrochemistry, and an X-ray diffraction study of (PCB)FeClCoCl, which shows the presence of a bound Cl- anion on the cobalt corrole…

Migration Reactivities of σ-Bonded Ligands of Organoiron and Organocobalt Porphyrins Depending on Different High Oxidation States

Migration reactivities of sigma-bonded organo-iron and -cobalt porphyrins were examined as a function of the compound oxidation state. Migration rates were determined for both the one-electron and two-electron oxidized species produced in the electron-transfer oxidation with different oxidants in acetonitrile at 298 K. The investigated compounds are represented as [(OETPP)Fe(R)](n)()(+), where n = 1 or 2, OETPP = the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin, and R = C(6)H(5), 3,5-C(6)F(2)H(3), or C(6)F(5), and as [(TPP)Co(R)](n)()(+), where n = 1 or 2, TPP = the dianion of 5,10,15,20-tetraphenylporphyrin, and R = CH(3) or C(6)H(5). The rapid two-electron oxid…

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO3CF3)

The metalation of several free base porphyrins by the bismuth salts Bi(NO3)3 and Bi(SO3CF3)3 in DMF or pyridine is described. The resulting stable Bi(III) porphyrin complexes are characterized by electrochemistry, 1H NMR and UV-vis spectroscopy. The structure of ( OEP ) Bi ( SO 3 CF 3) was also determined by single-crystal X-ray diffraction and shows that ( OEP ) Bi ( SO 3 CF 3) exists as a dimer which is stabilized by electrostatic interactions in which the two [(OEP)Bi]+ cations are linked via oxygen atoms of two symmetrically related [Formula: see text] anions, leading to a heptacoordinated bismuth center. Electrochemical oxidation of ( OEP ) Bi ( SO 3 CF 3) and ( T p TP ) Bi ( SO3CF3 )…

Electrochemistry and germanium porphyrins in nonaqueous media. Reactions of water and hydroxide ligands associated with (P)Ge(ClO4)2 and (P)Ge(OH)2, where P is the dianion of tetraphenylporphyrin (TPP) or octaethylporphyrin (OEP)

Ligand Noninnocence in Cobalt Dipyrrin–Bisphenols: Spectroscopic, Electrochemical, and Theoretical Insights Indicating an Emerging Analogy with Corroles

Three cobalt dipyrrin-bisphenol (DPPCo) complexes with different meso-aryl groups (pentafluorophenyl, phenyl, and mesityl) were synthesized and characterized based on their electrochemistry and spectroscopic properties in nonaqueous media. Each DPPCo undergoes multiple oxidations and reductions with the potentials, reversibility, and number of processes depending on the specific solution conditions, the specific macrocyclic substituents, and the type and number of axially coordinated ligands on the central cobalt ion. Theoretical calculations of the compounds with different coordination numbers are given in the current study in order to elucidate the cobalt-ion oxidation state and the innoc…

Electrochemical, Spectroelectrochemical, and Structural Studies of Mono- and Diphosphorylated Zinc Porphyrins and Their Self-Assemblies

International audience; Three series of porphyrins containing a Zn(II) central metal ion and zero, one or two phosphoryl groups at the meso-positions of the macrocycle were characterized as to their electrochemical, spectroscopic and structural properties in non-aqueous media. The investigated compounds are represented as 5,15-bis(4'-R-phenyl)porphyrinatozinc, 10-(diethoxyphosphoryl)-5,15-bis(4'-R-phenyl)porphyrinatozinc and 5,15-bis(diethoxyphosphoryl)-10,20-bis(4'-R-phenyl)porphyrinatozinc, where R = OMe, Me, H or CN. Linear-free energy relationships are observed between the measured redox potentials at room temperature and the electronic nature of the substituents at the 5 and 15 meso-ph…

Electrochemical and Spectroelectrochemical Studies of Diphosphorylated Metalloporphyrins. Generation of a Phlorin Anion Product

Two series of diphosphoryl-substituted porphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry in nonaqueous media containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The investigated compounds are 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrins (Ph)2(P(O)(OEt)2)2PorM and 5,15-bis(diethoxyphosphoryl)-10,20-di(para-carbomethoxyphenyl)porphyrins (PhCOOMe)2(P(O)(OEt)2)2PorM where M = 2H, Co(II), Ni(II), Cu(II), Zn(II), Cd(II), or Pd(II). The free-base and five metalated porphyrins with nonredox active centers undergo two ring-centered oxidations and two ring-centered reductions, the latter of which is followed by a chemical reaction of the por…

Synthesis and electrode reactions of difluorogermanium(IV) porphyrins. Molecular stereochemistry and crystal structure of difluoro-(2,3,7,8,12,13,17,18-octaethylporphyrinato)germanium(IV)

The difluorogermanium(IV) porphyrins [GeF2(P)][P = 2,3,7,8,12,13,17,18-octaethylporphyrinate(2–)(oep), 5,10,15,20-tetraphenylporphyrinate(2–)(tpp), or 5,10,15,20-tetra-p-tolylporphyrinate(2–)(tptp)] have been prepared by reacting hydrogen fluoride with the appropriate dichloro derivative [GeCl2(P)]. The complexes were characterized by elemental analysis, 1H n.m.r., i.r., and u.v.–visible spectroscopy. The electrochemical behaviour was investigated in non-aqueous media while spectroelectrochemistry and e.s.r. were used to characterize the oxidized and reduced complexes. Each complex could be reversibly oxidized or reduced by one electron. In each case these electron additions or abstractions…

Alkyl and Aryl Substituted Corroles. 1. Synthesis and Characterization of Free Base and Cobalt Containing Derivatives. X-ray Structure of (Me4Ph5Cor)Co(py)2

The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III) corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groups at the eight β-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-meso position of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The difference in potential between the first two oxidations is associated with the degree of interaction between the two corrole units of the dimer …

Cobalt(IV) corroles as catalysts for the electroreduction of O2: reactions of heterobimetallic dyads containing a face-to-face linked Fe(III) or Mn(III) porphyrin

Abstract A series of heterobinuclear cofacial porphyrin–corrole dyads containing a Co(IV) corrole linked by one of four different spacers in a face-to-face arrangement with an Fe(III) or Mn(III) porphyrin have been examined as catalysts for the electroreduction of O 2 to H 2 O and/or H 2 O 2 when adsorbed on the surface of a graphite electrode in air-saturated aqueous solutions containing 1 M HClO 4 . The examined compounds are represented as (PCY)M III ClCo IV Cl where P is a porphyrin dianion, C is a corrole trianion and Y is a biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or anthracene (A) spacer. The catalytic behavior of the seven investigated dyads in the two heterobimet…

Unusual Formation of a Stable 2D Copper Porphyrin Network

Copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, and UV-visible spectroscopy. Three crystalline forms were grown and studied by means of X-ray diffraction methods (single crystal and powder). The highly electron-withdrawing effect of phosphoryl groups attached directly to the porphyrin macrocycle results in a self-assembling process, with formation of a stable 2D coordination network, which is unusual for copper(II) porphyrins. The resulting 2D structure is a rare example of an assembly based on copper(II) porphyrins where the copper(II) central metal io…

First highly distorted π-extended Fe(II) porphyrin – a unique model to elucidate factors affecting the electrochemical potentials

The preparation, X-ray crystal structure and electrochemistry of a new poly-substituted air-stable tetrabenzoporphyrin iron(II) bis-pyridine complex (1) is reported.

Synthesis, electrochemistry, and spectroelectrochemistry of (P)Ge(Fc)2 and (P)Ge(C6H5)(Fc): first example of metal-carbon-.sigma.-bonded porphyrins with two different axial groups

Electrochemical and spectroelectrochemical studies of β-phosphorylated Zn porphyrins

The electrochemical and spectroelectrochemical properties of two β-phosphorylated Zn porphyrins, [2-diethoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (1) and [2-diisopropoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (2), are reported in CH 2 Cl 2 and PhCN containing tetrabutylammonium perchlorate (TBAP) or tetrabutylammonium hexafluorophosphate (TBAPF6) as supporting electrolyte. Under certain solution conditions, three one-electron reductions are observed, with the last process being attributed to the product of a chemical reaction following formation of the porphyrin dianion. Two or three oxidations are observed for the same compounds, again depending upon the solution c…

Three-Metal Coordination by Novel Bisporphyrin Architectures

The synthesis and characterization of a new type of bisporphyrin system is reported where the two macrocycles are linked in a cofacial arrangement by a substituted carbazole bridge. The three nitrogen atoms of the carbazole bridge in the compounds may complex a metal ion and thus provide a new parameter for varying the physical properties and flexibility of the dyad after formation of a three-metal system. In the present study, four bis-metalloporphyrin complexes were synthesized and examined by electrochemistry and thin-layer spectroelectrochemistry in CH(2)Cl(2) and PhCN. Two of the examined compounds contain Cu(II) or Zn(II) porphyrins and a carbazole linker with a bound Cu(II) ion, givi…

Synthesis and Electrochemical Reactivity of sigma-Bonded and N-Substituted Cobalt Porphycenes.

The first synthesis and characterization of sigma-bonded and N-substituted cobalt porphycenes is reported. The investigated compounds are represented as (Pc)Co(R) and (N-CH(3)OEPc)CoCl, where R is CH(3) or C(6)H(5), Pc is the dianion of 2,3,6,7,12,13,16,17-octaethylporphycene (OEPc), 2,7,12,17-tetrapropylporphycene (TPrPc), or 2,7,12,17-tetraethyl-3,6,13,16-tetramethylporphycene (EtioPc), N-CH(3)OEPc is the monoanion of N-methyl-2,3,6,7,12,13,16,17-octaethylporphycene. Each sigma-bonded (Pc)Co(R) derivative can be reversibly reduced or oxidized by two electrons, but a slow migration of the sigma-bonded R group occurs following electrogeneration of [(Pc)Co(R)](+)()(*)() leading, as a final p…

Reduzierte Geschwindigkeit des Elektronentransfers bei Mangan-Porphy- rinen mit verzerrter Konformation des Makrocyclus

Ein langsamer Elektronentransfer auf Mangan(III)-Porphyrine ist die Folge, wenn der Porphyrinmakrocyclus nicht planar ist. Dies konnte anhand kinetischer Messungen des homogenen Elektronentransfers von einer Reihe von Semichinon-Radikalanionen auf synthetische Manganporphyrine (siehe Formel, R1 = H, Cl, F; R2 = H, F) gezeigt werden. In drei der vier untersuchten Porphyrine ist der Makrocyclus nicht planar. Dieses Ergebnis konnte fur das Verstandnis der Rolle von Mangan in biologischen Elektronentransferprozessen wichtig sein.

Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads.

Three face-to-face linked porphyrin-corrole dyads were investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. The same three compounds were also investigated as to their ability to catalyze the electroreduction of dioxygen in aqueous 1 M HClO4 or HCl when adsorbed on a graphite electrode. The characterized compounds are represented as (PCY)H2Co, where P = a porphyrin dianion; C = a corrole trianion; and Y = a biphenylenyl, 9,9-dimethylxanthenyl, or anthracenyl spacer, which links the two macrocycles in a face-to-face arrangement. An axial binding of one or two Cl- ligands to the cobalt center of the corrole is …

Redox properties of nitrophenylporphyrins and electrosynthesis of nitrophenyl-linked Zn porphyrin dimers or arrays

Five nitrophenylporphyrins were investigated as to their electrochemical properties in CH 2 Cl 2 containing 0.1 M TBAP. The investigated compounds are represented as ( NO 2 Ph )x Ph 4-x PorM , where Por represents the dianion of the porphyrin macrocycle, Ph is a phenyl group on meso-position of the macrocycle, NO 2 Ph is a meso-substituted nitrophenyl group, M = 2 H , Pd II or Zn II and x = 1 or 2. Each porphyrin undergoes an initial one electron reduction at E1/2 = -1.07 to -1.12 V where the added negative charge is almost totally localized on the meso-nitrophenyl group of the compound. This reversible reduction is then followed by one or more irreversible reductions of the nitrophenyl an…

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

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 betw…

Synthesis, photochemistry, and electrochemistry of (P)Ge(R)2 and (P)Ge(R)X (P = TPP or OEP, R = CH3, CH2C6H5, or C6H5, and X = Cl-, OH-, or ClO4-)

Chaque complexe est caracterise par spectroscopie RMN de H1, UV-visible, IR et aussi par l'etude electrochimique

CCDC 902786: Experimental Crystal Structure Determination

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CCDC 1539258: Experimental Crystal Structure Determination

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CCDC 1578032: Experimental Crystal Structure Determination

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CCDC 990046: Experimental Crystal Structure Determination

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CCDC 902785: Experimental Crystal Structure Determination

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CCDC 1844989: Experimental Crystal Structure Determination

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CCDC 1880078: Experimental Crystal Structure Determination

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CCDC 1844993: Experimental Crystal Structure Determination

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CCDC 1812155: Experimental Crystal Structure Determination

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CCDC 1502145: Experimental Crystal Structure Determination

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CCDC 1890813: Experimental Crystal Structure Determination

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CCDC 1554869: Experimental Crystal Structure Determination

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CCDC 1844991: Experimental Crystal Structure Determination

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CCDC 990049: Experimental Crystal Structure Determination

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CCDC 990047: Experimental Crystal Structure Determination

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CCDC 902787: Experimental Crystal Structure Determination

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CCDC 990045: Experimental Crystal Structure Determination

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CCDC 1844992: Experimental Crystal Structure Determination

Related Article: Sergey E. Nefedov, Kirill P. Birin, Alla Bessmertnykh-Lemeune, Yulia Y. Enakieva, Anna A. Sinelshchikova, Yulia G. Gorbunova, Aslan Y. Tsivadze, Christine Stern, Yuanyuan Fang, Karl M. Kadish|2019|Dalton Trans.|48|5372|doi:10.1039/C9DT00706G

CCDC 1844990: Experimental Crystal Structure Determination

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CCDC 990048: Experimental Crystal Structure Determination

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CCDC 2194501: Experimental Crystal Structure Determination

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CCDC 1815709: Experimental Crystal Structure Determination

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CCDC 990050: Experimental Crystal Structure Determination

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