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 reduced in multiple one-electron-transfer steps, the first of which involves the M(III)/M(II) process of the porphyrin in the case of (PCY)MClCoCl and the Co(III)/Co(II) process of the corrole in the case of (PCY)H2Co. Each metal-centered redox reaction may be accompanied by the gain or loss of pyridine axial ligands, with the exact stoichiometry of the exchange process depending upon the specific combination of metal ions in the dyad, their oxidation states, and the particular spacer in the complex. Before this study was started, it was expected that the porphyrin-corrole dyads with the largest spacers, namely, O and A, would readily accommodate the formation of cobalt(III) bis-pyridine adducts because of the larger size of the cavity while dyads with the smallest B spacer would seem to have insufficient room to add even a single pyridine within the cavity, as was structurally seen in the case of (PCB)H2Co(py). This is clearly not the case, as shown in the present study. A reversible Co(III)/Co(II) reaction is seen for (PCB)MnClCoCl at -0.62 V, which when combined with spectroscopic data, leads to the assignment of (PCB)Mn(III)(py)2Co(III)(py) as the species in pyridine. The reduction of (PCB)Mn(III)(py)2Co(III)(py) to (PCB)Mn(II)(py)Co(III)(py) is accompanied on the slower spectroelectrochemical time scale by the appearance of a 603 nm band in the UV-vis spectra and is consistent with the addition of a second pyridine ligand to the Co(III)(py) unit of the dyad as one ligand is lost from the electrogenerated manganese(II) porphyrin, thus maintaining one pyridine ligand within the cavity. A different change in the coordination number is observed in the case of (PCB)FeClCoCl. Here the initial Fe(III) complex can be assigned as (PCB)Fe(III)ClCo(III)(py), which has no pyridine molecule within the cavity and the singly reduced form is characterized as (PCB)Fe(II)(py)2Co(III)(py)2, which contains two pyridine ligands inside the cavity. A following one-electron reduction of the Fe(II)/Co(III) complex then gives [(PCB)Fe(II)(py)2Co(II)]-.     

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 observed for singly and doubly oxidized (PCY)H2Co, with the exact stoichiometry of the reaction depending upon the spacer size and the concentration of Cl- added to solution. No Cl- binding occurs for the neutral or reduced forms of the dyad, which contrasts with what is seen for the monocorrole, (Me4Ph5Cor)Co, where a single Cl- ligand is added to the Co(III) corrole in PhCN. The Co(III) form of the corrole in (PCY)H2Co also appears to be the catalytically active species in the electroreduction of dioxygen, which occurs at potentials associated with the Co(IV)/Co(III) reaction, that is, 0.35 V in 1 M HClO4 as compared to 0.31-0.42 V for the same three dyads in PhCN and 0.1 M TBAP. The potential for the catalytic electroreduction of O2 in HCl shifts negatively by 60 to 70 mV as compared to E(1/2) values in 1 M HClO4, consistent with the binding of Cl- to the Co(IV) form of the corrole and its rapid dissociation after electroreduction to Co(III) at the electrode surface.     

Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis,properties and DFT calculations

Ethynyl-bridged porphyrin-corrole dyads and triads were synthesized by using Pd(0) mediated coupling reactions and their structures were characterized by NMR, FT-IR, UV/Vis and fluorescence techniques. Besides spectroscopic techniques, computational studies at B3LYP/6-311G(d,p) level of DFT were also used to elucidate the minimum energy geometries and the molecular orbital characteristics of the new dyads and triads. DFT calculations pointed out the presence of charge separated donor-acceptor property between macrocycles of dyads and triads, and the emission studies indicated an excited state interaction between macrocycles, and energy transfer from the porphyrin to the corrole unit.     

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 corrole macrocycle, when linked to another copper corrole or copper(II) porphyrin, can be considered to be a Cu(III) complex in equilibrium with a Cu(II) radical species, copper(III) corrole being the main oxidation state of the corrole species at all temperatures. The cofacial orientation of (BCB)Cu(2), (BCA)Cu(2), and (PCB)Cu(2) was confirmed by X-ray crystallography. Structural data: (BCB)Cu(2)(C(110)H(82)N(8)Cu(2).3CDCl(3)), triclinic, space group P, a = 10.2550(2) A, b = 16.3890(3) A, c = 29.7910(8) A, alpha = 74.792(1) degrees , beta = 81.681(1) degrees , gamma = 72.504(2) degrees , Z = 2; (BCA)Cu(2)(C(112)H(84)N(8)Cu(2).C(7)H(8).1.5H(2)O), monoclinic, space group P 2(1)/c, a = 16.0870(4) A, b = 35.109(2) A, c = 19.1390(8) A, beta = 95.183(3) degrees , Z = 4; (PCB)Cu(2)(C(89)H(71)N(8)Cu(2).CHCl(3)), monoclinic, space group P2(1)/n, a = 16.7071(3) A, b = 10.6719(2) A, c = 40.8555(8) A, beta = 100.870(1) degrees , Z = 4. The two cofacial biscorroles, (BCA)Cu(2) and (BCB)Cu(2), both show three electrooxidations under the same solution conditions. The reduction of (BCA)Cu(2) involves a reversible electron addition to each macrocycle at the same potential of E(1/2) = -0.20 V although (BCB)Cu(2) is reversibly reduced in two steps to give first [(BCB)Cu(2)](-) and then [(BCB)Cu(2)](2)(-), each of which was characterized by ESR spectroscopy as containing a Cu(II) center. These latter electrode reactions occur at E(1/2) = -0.36 and -0.51 V versus a saturated calomel reference electrode. The half-reduced and fully reduced (BCB)Cu(2) show similar Cu(II) ESR spectra, and no evidence of a triplet signal is observed. The two well-separated reductions of (BCB)Cu(2) to give [(BCB)Cu(2)](2)(-) can be attributed to a stronger pi-pi interaction between the two macrocycles of this dimer as compared to those of (BCA)Cu(2). The copper porphyrin-corrole dyads, (PCA)Cu(2) and (PCB)Cu(2), show five reversible oxidations and two reversible reductions, and these potentials are compared with corresponding values for electrochemical reactions of the porphyrin and corrole monomers under the same solution conditions.     

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. The electrochemical and spectroscopic data on these new bismacrocycles are compared to those of previously reported biscorroles of the type (BCA)Co(2) and (BCB)Co(2). The CO and/or pyridine binding properties of each biscorrole and porphyrin-corrole in CH(2)Cl(2) are also presented. Only one CO ligand is bound axially to each corrole unit of the bismacrocycle but five- and six-coordinate pyridine complexes can be generated for the same compounds, with the exact stoichiometry depending upon the concentration of pyridine in solution. In all cases, the six-coordinate bispyridine corrole complex can be unambiguously identified by a strong diagnostic marker band located at 598-601 nm. The formation constants for pyridine binding to the biscorroles range from log K(1) = 3.14 to 5.08 while log K(2) ranges from 1.10 to 2.61 depending upon the specific spacer. Carbon monoxide binding constants range from log K = 3.6 to 4.0 in the case of the biscorroles and from log K = 3.4 to 4.1 in the case of the porphyrin-corrole dyads. These values also depend on the specific spacer in the complex and, like the pyridine binding constants, decrease in the order BCO > BCA > BCB for the biscorroles and PCO > PCA > PCB for the porphyrin-corrole complexes.     

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. Structural data: (PCB)FeClCoCl x 0.5(C7H16) x 0.5(CH2Cl2) x 2H2O, triclinic, space group P1, a = 13.8463(3) A, b = 16.8164(5) A, c = 17.9072(6) A, alpha = 93.780(1) degrees, beta = 111.143(1) degrees, gamma = 97.463(2) degrees, Z = 2.     

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 (-) anions were shown to bind axially in a stepwise addition to give the five- and six-coordinate complexes in nonaqueous media. In each case, complexation with one or two anionic axial ligands led to an easier oxidation and a harder reduction as compared to the uncomplexed four-coordinate species.     

Photochemical and electrochemical properties of zinc chlorin-C60 dyad as compared to corresponding free-base chlorin-C60, free-base porphyrin-C60, and zinc porphyrin-C60 dyads.

The photochemical and electrochemical properties of four chlorin-C60 or porphyrin-C60 dyads having the same short spacer between the macrocycle and the fullerene are examined. In contrast with all the previous results on porphyrin-fullerene dyads, the photoexcitation of a zinc chlorin-C60 dyad results in an unusually long-lived radical ion pair which decays via first-order kinetics with a decay rate constant of 9.1 x 10(3) x s(-1). This value is 2-6 orders of magnitude smaller than values reported for all other porphyrin or chlorin donor-acceptor of the molecule dyad systems. The formation of radical cations of the donor part and the radical anion of the acceptor part was also confirmed by ESR measurements under photoirradiation at low temperature. The photoexcitation of other dyads (free-base chlorin-C60, zinc porphyrin-C60, and free-base porphyrin-C60 dyads) results in formation of the ion pairs which decay quickly to the triplet excited states of the chlorin or porphyrin moiety via the higher lying radical ion pair states as is expected from the redox potentials.     

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

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 might also transport and/or activate dioxygen. In the present paper, we report the stepwise synthesis and characterisation of a cofacial porphyrin–corrole bearing an anthracenyl bridge, (PCA)H₅ where PCA is the pentaanion of 1-(13,17-diethyl-2,3,7,8,12,18-hexamethylporphyrin–5-yl)-8-(7,8,12,13-tetramethyl-2,3,17,18-tetraphenylcorrol-10-yl) anthracene. The synthesis and characterisation of the μ-superoxo Co(III)/Co(III) complex 〚(PCA)Co₂Im₂〛(μ-O₂) is also described.     

First Synthesis of a Binuclear [Mn(II)(bipy)-Fe(III)(porphyrin)] Complex: Spectroscopic Characterization and First Evidence of Reversible Formation of Manganese(III) as Manganese Peroxidase

A [(P)Fe(III)-Mn(II)] bimetallic complex, mimicking the active site of manganese peroxidase, has been synthesized. A modified highly fluorinated porphyrin, 5,10,15-tris(pentafluorophenyl)-20-(o-aminophenyl)porphyrin, has been used to introduce, through a short spacer linked to the amino function, a manganese auxiliary ligand, 6-aminomethyl-2,2'-bipyridine. Two successive metalations by FeCl(2) and MnCl(2) afforded the [(P)Fe(III)-Mn(II)] bimetallic complex that has been characterized by elemental analysis and FAB(+) mass spectrometry. X-band EPR spectroscopy and magnetic susceptibility measurements were in agreement with two high spin Fe(III) and Mn(II) centers without magnetic exchange interaction. Moreover, there is no higher intermolecular association through &mgr;-chloro bridging as observed by EPR with a simpler chloromanganese complex, Mn(bipy)(2)Cl(2), at high concentration. Addition of pentafluoroiodosobenzene in methanol at 0 degrees C led to the progressive and complete disappearance of the EPR Mn(II) signals, that were recovered after addition of a phenol. This result is consistent with Mn(III) formation. This production of Mn(III) requires the presence of the iron porphyrin and is proposed to occur through the intermediate formation of a Fe(IV) dimethoxide species which can be related to the oxidation of Mn(II) catalyzed by manganese peroxidase compound II.     

CO2 photoreduction with long-wavelength light: dyads and monomers of zinc porphyrin and rhenium bipyridine

Photocatalytic CO(2) reduction has been studied for two dyads with porphyrin covalently attached to rhenium tricarbonyl bipyridine moieties, and on separate components consisting of [Re(CO)(3)(Picoline)Bpy](+) and either zinc porphyrin or zinc chlorin. TONs decrease in the order: zinc porphyrin + Re > long spacer dyad > zinc chlorin + Re > short spacer dyad.     

Ligand-field dependence of the excited state dynamics of Hangman bisporphyrin dyad complexes

A new Hangman porphyrin architecture has been developed to interrogate the ligand-field dependence of photoinduced PCET versus excitation energy transfer and intersystem crossing in PZn(II)-PFe(III)-OH dyads (P = porphyrin). In this design, a hanging carboxylic acid group establishes a hydrogen-bonding network to anchor the weak-field OH- ligand in the distal site of the PFe(III)-OH acceptor, whereas the proximal site is left available to accept strong-field imidazole ligands. Thus, controlling the tertiary coordination environment gives access to the first synthetic example of a porphyrin dyad with a biologically relevant weak-field/strong-field configuration of axial ligands at the heme. Transient absorption spectroscopy has been employed to probe the fate of the initial PZn(II)-based S1 excited state, revealing rapid S1 quenching for all dyads in the presence and absence of strong-field imidazole ligands (tau = 6-50 ps). The absence of a (P*+)Zn(II) signal that would complement photoinduced PCET at the PFe(III)-OH subunit (i.e., PFe(III)-OH --> PFe(II)-OH2) shows that excitation energy transfer and intersystem crossing channels dominate the quenching, regardless of whether proximal strong field ligands are present. Moreover, this photophysical assignment is independent of the solvent dielectric constant and whether a phenylene or biphenylene spacer is used to span the two porphyrin subunits. Electronic structure calculations suggest that the structural reorganization attendant to reductive PCET at the high-spin Fe(III)-OH center imposes a severe kinetic cost that can only be alleviated by inducing a low-spin electronic configuration with two strong-field axial ligands.     

Through Bridge Spin Coupling in Homo- and Heterobimetallic Porphyrin Dimers upon Stepwise Oxidations: A Spectroscopic and Theoretical Investigation

We have described copper(II)-iron(III) and copper(II)-manganese(III) heterobimetallic porphyrin dimers and compared them with the corresponding homobimetallic analogs. UV-visible spectra are very distinct in the heterometallic species while electrochemical studies demonstrate that these species, as compared to the homobimetallic analog, are much easier to oxidize. Combined Mössbauer, EPR, NMR, magnetic and UV-visible spectroscopic studies show that upon 2e-oxidation of the heterobimetallic complexes only ring-centered oxidation occurs. The energy differences between HOMO and LUMO are linearly dependent with the low-energy NIR band obtained for the 2e-oxidized complexes. Also, strong electronic communication between two porphyrin rings through the bridge facilitates coupling between various unpaired spins present while the coupling model depends on the nature of metal ions used. While unpaired spins of Fe(III) and the porphyrin π-cation radical are strongly antiferromagnetically coupled, such coupling is rather weak between Mn(III) and a porphyrin π-cation radical. Moreover, the coupling between two π-cation radicals are much stronger in the 2e-oxidized complexes of dimanganese(III) and copper(II)-manganese(III) porphyrin dimers as compared to their diiron(III) and copper(II)-iron(III) analogs. Furthermore, coupling between the unpaired spins of a π-cation radical and copper(II) is much stronger in the 2e-oxidized complex of copper(II)-iron(III) porphyrin dimer as compared to its copper(II)-manganese(III) analog. The Mulliken spin density distributions in 2e-oxidized homo- and heterobimetallic complexes show symmetric and asymmetric spread between the two macrocycles, respectively. In both the 2e-oxidized heterobimetallic complexes, the Cu(II) porphyrin center acts as a charge donor while Fe(III)/Mn(III) porphyrin center act as a charge acceptor. The experimental observations are also strongly supported by DFT calculations.     

Synthesis and properties of covalently linked BF2–oxasmaragdyrin–porphyrin dyads and triad

Two covalently linked diphenyl ethyne bridged unsymmetrical dyads containing porphyrin and BF₂–oxasmaragdyrin and Zn(II)porphyrin and BF₂–oxasmaragdyrin units and one covalently linked triad containing Zn(II)porphyrin, porphyrin and BF₂–oxasmaragdyrin units were synthesized by coupling appropriate functionalized macrocycles under Pd(0) coupling reaction conditions. The dyads and triad were freely soluble in common organic solvents and confirmed by ES-MS spectra. 1D and 2D NMR techniques were used to characterize the dyads and triad. Absorption and electrochemical studies of dyads and triad showed the overlapping features of the constituted macrocycles indicating that the macrocycles retain their basic features in the dyads and triad. The BF₂–oxasmaragdyrin absorbs at lower energy and emits strongly in the visible region compared to porphyrin/Zn(II)porphyrin. Thus, BF₂–oxasmaragdyrin acts as energy acceptor and porphyrin/Zn(II) porphyrin act as energy donor in dyads and triad. The steady state and time-resolved fluorescence studies supported an efficient energy transfer from porphyrin/Zn(II)porphyrin to BF₂–oxasmaragdyrin unit in dyads and triad.     

Origin of d‐π Interaction in Cobalt(II) Porphyrins under Synergistic Effects of Core Contraction and Axial Ligation: Implications for a Ligand Effect of Natural Distorted Tetrapyrrole

The reactivity of the metalloporphyrins was closely related to their ligand effect at axial position. The electronic properties of six model Co(II) porphyrins are investigated by spectral and electrochemical methods. Structural parameters of the Co(II) complexes are directly obtained from their crystal structures. We demonstrate that the unpaired 3d electron of low‐spin Co(II) ions in nonplanar Co(II) porphyrin complexes activated by core contraction of porphyrin macrocycles can be further activated by the axial ligation of imidazole. The activated electron can combine with a π orbital of the porphyrin ring to form a new d‐π orbital, which can induce the Q‐band of Co(II) porphyrins to visibly split. Addition of imidazole causes the Co(II)/Co(III) and Co(II)/Co(I) reactions to shift to more negative potential. Our results indicate that strong axial ligation and core contraction both play important roles in electron transfer in redox catalysis involving Co(II) complexes.     

Synthesis and properties of a new (octaethylporphyrinato)-manganese(III)–pyridinyl-substituted pyrrolidinofullerene dyad

The formation of a porphyrin–fullerene dyad from 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-3-ylmethyl)-2′,5′-dihydro-1′H-pyrrolo[3′,4′: 1,9](C₆₀-I_h)[5,6]fullerene and (2,3,7,8,12,13,17,18-octaethylporphyrinato) manganese(III) with axial chloride ligand has been studied on a quantitative level with the goal of obtaining supramolecules possessing biological activity. Preliminarily, the reaction of manganese(III) porphyrin with pyridine has been studied. The donor–acceptor dyads are formed either instantaneously and reversibly (pyridine) or slowly and irreversibly (substituted fullerene). In both cases, the reaction is a one-step process for which thermodynamic and kinetic parameters have been determined. The results can be used to optimize conditions for the synthesis of porphyrin–fullerene dyads. The obtained dyads have been characterized by spectral data and stability constants.     

Nitrogen atom transfer between manganese complexes of salen, porphyrin, and corrole and characterization of a (nitrido)manganese(VI) corrole

The investigations of complete nitrogen atom transfer reactions from (nitrido)manganese(V) salen to manganese(III) complexes of porphyrins and corroles revealed that stabilization of the [Mn(N)]2+ moiety is in the order of corrole > porphyrin > salen. The first kinetic examination of this quite fundamental reaction exposed a large solvent effect on both the enthalpy and entropy activation energies. Oxidation of the (nitrido)manganese(V) corroles leads to the first (nitrido)manganese(VI) complexes that are coordinated by tetrapyrrolic ligands.     

氯离子存在下四苯基卟啉合锰的电化学和现场光谱电化学II. 氧化过程

本文研究了氯离子滴定过程中四苯基卟啉合锰氧化过程的常规循环伏安、薄层循环伏安及现场紫外-可见光谱电化学行为。发现在1摩尔比的Cl^-存在下, 四苯基卟啉合锰经历了Mn(III)/Mn(III)环阳离子自由基及进一步氧化为环两价阳离子的过程, 并伴随有异卟啉生成的后行化学反应, 当2摩尔比的Cl^-存在时, 反应机理转变为Mn(III)/Mn(IV), Mn(IV)/Mn(IV)环阳离子自由基并伴随有异卟啉生成反应的两个氧化步骤。提出了与这一滴定过程相关的氧化还原反应机理。     

Multireversible redox processes in pentanuclear bis(triple-helical) manganese complexes featuring an oxo-centered triangular {Mn(II)2Mn(III)(μ3-O)}5+ or {Mn(II)Mn(III)2(μ3-O)}6+ core wrapped by two {Mn(II)2(bpp)3}-

A new pentanuclear bis(triple-helical) manganese complex has been isolated and characterized by X-ray diffraction in two oxidation states: [{Mn(II)(μ-bpp)(3)}(2)Mn(II)(2)Mn(III)(μ-O)](3+) (1(3+)) and [{Mn(II)(μ-bpp)(3)}(2)Mn(II)Mn(III)(2)(μ-O)](4+) (1(4+)). The structure consists of a central {Mn(3)(μ(3)-O)} core of Mn(II)(2)Mn(III) (1(3+)) or Mn(II)Mn(III)(2) ions (1(4+)) which is connected to two apical Mn(II) ions through six bpp(-) ligands. Both cations have a triple-stranded helicate configuration, and a pair of enantiomers is present in each crystal. The redox properties of 1(3+) have been investigated in CH(3)CN. A series of five distinct and reversible one-electron waves is observed in the -1.0 and +1.50 V potential range, assigned to the Mn(II)(4)Mn(III)/Mn(II)(5), Mn(II)(3)Mn(III)(2)/Mn(II)(4)Mn(III), Mn(II)(2)Mn(III)(3)/Mn(II)(3)Mn(III)(2), Mn(II)Mn(III)(4)/Mn(II)(2)Mn(III)(3), and Mn(III)(5)/Mn(II)Mn(III)(4) redox couples. The two first oxidation processes leading to Mn(II)(3)Mn(III)(2) (1(4+)) and Mn(II)(2)Mn(III)(3) (1(5+)) are related to the oxidation of the Mn(II) ions of the central core and the two higher oxidation waves, close in potential, are thus assigned to the oxidation of the two apical Mn(II) ions. The 1(4+) and 1(5+) oxidized species and the reduced Mn(4)(II) (1(2+)) species are quantitatively generated by bulk electrolyses demonstrating the high stability of the pentanuclear structure in four oxidation states (1(2+) to 1(5+)). The spectroscopic characteristics (X-band electron paramagnetic resonance, EPR, and UV-visible) of these species are also described as well as the magnetic properties of 1(3+) and 1(4+) in solid state. The powder X- and Q-band EPR signature of 1(3+) corresponds to an S = 5/2 spin state characterized by a small zero-field splitting parameter (|D| = 0.071 cm(-1)) attributed to the two apical Mn(II) ions. At 40 K, the magnetic behavior is consistent for 1(3+) with two apical S = 5/2 {Mn(II)(bpp)(3)}(-) and one S = 2 noninteracting spins (11.75 cm(3) K mol(-1)), and for 1(4+) with three S = 5/2 noninteracting spins (13.125 cm(3) K mol(-1)) suggesting that the {Mn(II)(2)Mn(III)(μ(3)-O)}(5+) and {Mn(II)Mn(III)(2)(μ(3)-O)}(6+) cores behave at low temperature like S = 2 and S = 5/2 spin centers, respectively. The thermal behavior below 40 K highlights the presence of intracomplex magnetic interactions between the two apical spins and the central core, which is antiferromagnetic for 1(3+) leading to an S(T) = 3 and ferromagnetic for 1(4+) giving thus an S(T) = 15/2 ground state.     

Synthesis of oligo(p-phenylene)-linked dyads containing free base, zinc(II) or thallium(III) porphyrins for studies in artificial photosynthesis

A series of (p-phenylene)_n-linked meso-mesityl-substituted porphyrin dyads (n=2-4) was prepared via Suzuki coupling of zinc(II) and free base porphyrin building blocks. The resulting zinc(II)/free base porphyrin dyads were demetalated. The series of free base porphyrin dimers (n=1-4), four other porphyrin dimers (with p-phenylene, diphenylethyne or diphenylbutadiyne linkers; and aryl or tridec-7-yl meso substituents), and several benchmark monomers were converted to the thallium(III)chloride complexes under mild conditions. The collection of eight Tl(III)Cl/Tl(III)Cl dimers is designed for studies of ground-state hole-transfer processes and comparison with the excited-state energy- and hole-transfer processes of the corresponding Zn(II)/free base dyads. Altogether, 18 new porphyrin arrays and benchmark monomers have been prepared.