Electronic Coupling and Electrocatalysis in Redox Active Fused Iron Corroles.

Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a ß,ß-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [H3tpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [FeIIItpfc(py)]2COT and 6-coordinate [FeIIItpfc(py)2]2COT, with one and two axial pyridine ligands per metal, respectively. X-Ray crystallography reveals a dome-shaped structure for [FeIIItpfc(py)]2COT and a perfectly planar geometry which (surprisingly at first) is also characterized by shorter Fe-N (corrole) and Fe-N (pyridine) distances. Computational investigations clarify that the structural phenomena are due to a change in the iron(III) spin state from intermediate (S = 3/2) to low (S = 1/2), and that both the 5- and 6-coordinated complexes are enthalpically favored. Yet, in contrast to iron(III) porphyrins, the formation enthalpy for the coordination of the first pyridine to Fe(III) corrole is more negative than that of the second pyridine coordination. Possible interactions between the two corrole subunits and the chelated iron ions were examined by UV-Vis spectroscopy, electrochemical techniques, and density functional theory (DFT). The large differences in the electronic spectra of the dimer relative to the monomer are concluded to be due to a reduced electronic gap, owing to the extensive electron delocalization through the fusing bridge. A cathodic sweep for the dimer discloses two redox processes, separated by 230 mV. The DFT self-consistent charge density for the neutral and cationic states (1- and 2-electron oxidized) reveals that the holes are localized on the macrocycle. A different picture emerges from the reduction process, where both the electrochemistry and the calculated charge density point toward two consecutive electron transfers with similar energetics, indicative of very weak electron communication between the two redox active iron(III) sites. The binuclear complex was determined to be a much better catalyst for the electrochemical hydrogen evolution reaction (HER) than the analogous mononuclear corrole.

Chromium Complexes with Oxido and Corrolato Ligands: Metal-Based Redox Processes versus Ligand Non-Innocence.

Metal- versus ligand-centered redox processes and the effects of substituents on the ligands on the spectroscopic properties of the metal complexes are at the heart of research on metal complexes with non-innocent ligands. This work presents three examples of chromium complexes that contain both oxido and corrolato ligands, with the substituents on the corrolato ligands being different in the three cases. Combined X-ray crystallographic, electrochemical, UV/Vis/NIR/EPR spectroelectrochemical, and EXAFS/XANES measurements, together with DFT calculations, have been used to probe the complexes in three different redox forms. This combined approach makes it possible to address questions related to chromium- versus corrolato-centered redox processes, and the accessibility (or not) of CrIV , CrV , and CrVI in these complexes, as well as their spin states. To the best of our knowledge, these are the first EXAFS/XANES investigations on Cr-corrolato complexes in different redox forms, and hence these data should set benchmarks for future investigations on such complexes by this method.

Reactive Intermediates Involved in Cobalt Corrole Catalyzed Water Oxidation (and Oxygen Reduction).

A detailed investigation of the cobalt corrole Co(tpfc) as molecular catalyst for electrochemical water oxidation uncovered many important mechanism-of-action details that are crucial for the design of optimally performing systems. This includes the identification of the redox states that do and do not participate in catalysis and very significant axial ligand effects on the activity of the doubly oxidized complex. Specifics deduced for the electrocatalysis under homogeneous conditions include the following: the one-electron oxidation of the cobalt(III) corrole is completely unaffected by reaction conditions; catalysis coincides with the second oxidation event; two catalytic waves develop in the presence of OH-, and the one at lower overpotential is dominant under more basic conditions. Comparative spectroelectrochemical measurements performed for Co(tpfc) and Al(tpfc), the analogous corrole chelated by the nonredox active aluminum, revealed that the second oxidation process of Co(tpfc) is much more significantly metal-centered than the first one. EPR studies revealed that shift from fully corrole-centered to partially metal-centered in the singly oxidized complex [Co(tpfc)]+ is achievable with fluoride as axial ligand. The analogous experiment, but with hydroxide instead of fluoride, could not be performed because of a surprising phenomenon: formation of a cobalt-superoxide complex that is actually relevant to oxygen reduction rather than to water oxidation. Nevertheless, fluoride and hydroxide induce very similar effects in terms of the appearance of two catalytic waves, lowering of onset potentials, and increasing the catalytic activity. The main conclusions from the accumulated data are that the apparent pH effect is actually due to hydroxide binding to the cobalt center and that π-donating axial ligands play pivotal and beneficial roles regarding the main factors that are important for facilitating the oxidation of water.

Isovalent AgIII /AgIII , AgII /AgII , Mixed-Valent AgII /AgIII , and Corrolato-Based Mixed-Valency in ß,ß'-Linked [Bis{corrolato-silver}]n Complexes.

Mixed-valent compounds are fascinating entities that are useful as models for investigating electron-transfer reactions, and find use in a host of biologically relevant redox processes. Though the bio-relevant metal copper is well established in mixed-valent chemistry, the AgII /AgIII mixed-valent combination of its higher congener in a molecular complex has rarely been reported before. This work reports the synthesis of a new ß,ß'-linked bis{corrolato-silver(III)} complex and its characterization in five different redox states. A combination of electrochemistry, spectroelectrochemistry, and DFT calculations point to the existence of a mixed-valent AgII /AgIII and an isovalent AgII /AgII form. Additionally, characterization of the AgIII /AgIII form and ligand-based corrolato-centered mixed-valency is presented as well. These results thus open new avenues for bis-corrolato ligands and for mixed-valency in disilver compounds.

Ruthenium-Ruthenium-Bonded [Bis{corrolato-ruthenium(III)}]n (n=0, +1, -1) Complexes: Model Compounds for the Photosynthetic Special Pair.

We present herein the synthesis of three new bis(corrolato-ruthenium(III)) complexes containing unsupported Ru-Ru bonds and their characterization in different redox states. The 1 H NMR spectra of the bis(corrolato-ruthenium(III)) complexes displayed "normal" chemical shifts and the compounds proved to be EPR-silent. Crystallographic characterization of the dimers indicated Ru-Ru distances of 2.175 Å, consistent with a triple bond between the two ruthenium centers. All of the synthesized complexes undergo two successive reversible oxidations and a single reversible reduction. A combination of UV/Vis/NIR/EPR spectroelectrochemical studies and DFT calculations established the redox state distributions in these ruthenium-ruthenium-bonded dimers. Whereas reduction of the dimers is metal-based and leads to metal-metal-bonded mixed-valent RuII -RuIII species, one-electron oxidation largely retains the RuIII -RuIII situation with the generation of metal-bound corrolato radicals. The present study thus concerns the first UV/Vis/NIR/EPR spectroelectrochemical characterization and DFT calculations of ruthenium-ruthenium-bonded rotationally ordered corrole dimers. The mean plane separation between the two corrole units in these dimers is around 3.543 Å, which is in close agreement to that in the "special pair" in chlorophyll. Oxidation of these ruthenium-ruthenium-bonded dimers gives rise to two new electronic absorption bands in the NIR region (similar to those of the special pair), which have apparently not been mentioned/observed in earlier reports on ruthenium-ruthenium-bonded corrole dimers. These bands mainly originate from inter-corrole transitions.

Experimental and Theoretical Investigations of the Existence of Cu(II), Cu(III), and Cu(IV) in Copper Corrolato Complexes.

The most common oxidation states of copper in stable complexes are +I and +II. Cu(III) complexes are often considered as intermediates in biological and homogeneous catalysis. More recently, Cu(IV) species have been postulated as possible intermediates in oxidation catalysis. Despite the importance of these higher oxidation states of copper, spectroscopic data for these oxidation states remain scarce, with such information on Cu(IV) complexes being non-existent. We herein present the synthesis and characterization of three copper corrolato complexes. A combination of electrochemistry, UV/Vis/NIR/EPR spectroelectrochemistry, XANES measurements, and DFT calculations points to existence of three distinct redox states in these molecules for which the oxidation states +II, +III, and +IV can be invoked for the copper centers. The present results thus represent the first spectroscopic and theoretical investigation of a Cu(IV) species, and describe a redox series where Cu(II), Cu(III), and Cu(IV) are discussed within the same molecular platform.

Silver corrole complexes: unusual oxidation states and near-IR-absorbing dyes.

Macrocycles such as porphyrins and corroles have important functions in chemistry and biology, including light absorption for photosynthesis. Generation of near-IR (NIR)-absorbing dyes based on metal complexes of these macrocycles for mimicking natural photosynthesis still remains a challenging task. Herein, the syntheses of four new Ag(III) corrolato complexes with differently substituted corrolato ligands are presented. A combination of structural, electrochemical, UV/Vis/NIR-EPR spectroelectrochemical, and DFT studies was used to decipher the geometric and electronic properties of these complexes in their various redox states. This combined approach established the neutral compounds as stable Ag(III) complexes, and the one-electron reduced species of all the compounds as unusual, stable Ag(II) complexes. The one-electron oxidized forms of two of the complexes display absorptions in the NIR region, and thus they are rare examples of mononuclear complexes of corroles that absorb in the NIR region. The appearance of this NIR band, which has mixed intraligand charge transfer/intraligand character, is strongly dependent on the substituents of the corrole rings. Hence, the present work revolves round the design principles for the generation of corrole-based NIR-absorbing dyes and shows the potential of corroles for stabilizing unusual metal oxidation states. These findings thus further contribute to the generation of functional metal complexes based on such macrocyclic ligands.

Synthesis, spectral characterization, structures, and oxidation state distributions in [(corrolato)Fe(III)(NO)](n) (n = 0, +1, -1) complexes.

Two novel trans-A2B-corroles and three [(corrolato){FeNO}(6)] complexes have been prepared and characterized by various spectroscopic techniques. In the native state, all these [(corrolato){FeNO}(6)] species are diamagnetic and display "normal" chemical shifts in the (1)H NMR spectra. For two of the structurally characterized [(corrolato){FeNO}(6)] derivatives, the Fe-N-O bond angles are 175.0(4)° and 171.70(3)° (DFT: 179.94°), respectively, and are designated as linear nitrosyls. The Fe-N (NO) bond distances are 1.656(4) Å and 1.650(3) Å (DFT: 1.597 Å), which point toward a significant Fe(III) → NO back bonding. The NO bond lengths are 1.159(5) Å and 1.162(3) Å (DFT: 1.162 Å) and depict their elongated character. These structural data are typical for low-spin Fe(III). Electrochemical measurements show the presence of a one-electron oxidation and a one-electron reduction process for all the complexes. The one-electron oxidized species of a representative [(corrolato){FeNO}(6)] complex exhibits ligand to ligand charge transfer (LLCT) transitions (cor(π) → cor(π*)) at 399 and 637 nm, and the one-electron reduced species shows metal to ligand charge transfer (MLCT) transition (Fe(dπ) → cor(π*)) in the UV region at 330 nm. The shift of the νNO stretching frequency of a representative [(corrolato){FeNO}(6)] complex on one-electron oxidation occurs from 1782 cm(-1) to 1820 cm(-1), which corresponds to 38 cm(-1), and on one-electron reduction occurs from 1782 cm(-1) to 1605 cm(-1), which corresponds to 177 cm(-1). The X-band electron paramagnetic resonance (EPR) spectrum of one-electron oxidation at 295 K in CH2Cl2/0.1 M Bu4NPF6 displays an isotropic signal centered at g = 2.005 with a peak-to-peak separation of about 15 G. The in situ generated one-electron reduced species in CH2Cl2/0.1 M Bu4NPF6 at 295 K shows an isotropic signal centered at g = 2.029. The 99% contribution of corrole to the HOMO of native species indicates that oxidation occurs from the corrole moiety. The results of the electrochemical and spectroelectrochemical measurements and density functional theory calculations clearly display a preference of the {FeNO}(6) unit to get reduced during the reduction step and the corrolato unit to get oxidized during the anodic process. Comparisons are presented with the structural, electrochemical, and spectroelectrochemical data of related compounds reported in the literature, with a particular focus on the interpretation of the EPR spectrum of the one-electron oxidized form.

Superstructured metallocorroles for electrochemical CO2 reduction.

Cobalt and iron complexes of corroles with tyrosine-like proton-transfer-relay moieties in proximity to the metal center have been prepared and fully characterized. The (nitrosyl)iron complex performs very well as an electrocatalyst for the reduction of CO2 to CO.

Structural, electrochemical and spectroelectrochemical study on the geometric and electronic structures of [(corrolato)Au(III)](n) (n = 0, +1, -1) complexes.

Synthesis of two new Au(III) corrole complexes with unsymmetrically substituted corrole ligands is presented here. The newly synthesized Au-compounds have been characterized by various spectroscopic techniques. The structural characterization of a representative Au(III) corrole has also been possible. Electrochemical, UV-vis-NIR/EPR spectroelectrochemical and DFT studies have been used to decipher the electronic structures of various electro-generated species. These are the first UV-vis-NIR/EPR spectroelectrochemical investigations on Au(III) corroles. Assignment of redox states of electro-generated Au(III) corroles is supported by DFT analysis. In contrast to the metal centered reduction reported in Au(III) porphyrins, one electron reduction in Au(III) corroles has been assigned to corrole centered on the basis of experimental and theoretical studies. Thus, the Au(III) corroles (not the analogous Au(III) porphyrin derivatives!) bear a truly redox inactive Au(III) center. Additionally, these Au-corrole complexes display NIR electrochromism, the origin of which is all on corrole-centered processes.

NIR-emissive iridium(III) corrole complexes as efficient singlet oxygen sensitizers.

Three new iridium(iii) corrole complexes, having symmetrically and asymmetrically substituted corrole frameworks and judiciously varied axial ligands are prepared and characterized by various spectroscopic techniques including the X-ray structures of two of them. The observed phosphorescence at ambient temperature appears at much longer wavelengths than the previously reported Ir(iii) porphyrin/corrole derivatives. Efficiencies of these compounds in the generation of singlet oxygen are also studied for the first time.

Semi-insulating behaviour of self-assembled tin(IV)corrole nanospheres.

Three novel tin(iv)corrole complexes have been prepared and characterized by various spectroscopic techniques including single crystal X-ray structural analysis. Packing diagrams of the tin(iv)corroles revealed that corrolato-tin(iv)-chloride molecules are interconnected by intermolecular C-HCl hydrogen bonding interactions. HCl distances are 2.848 Å, 3.051 Å, and 2.915 Å, respectively, for the complexes. In addition, the C-HCl angles are 119.72°, 144.70°, and 147.08°, respectively, for the complexes. It was also observed that in one of the three synthesized complexes dimers were formed, while in the other two cases 1D infinite polymer chains were formed. Well-defined and nicely organized three-dimensional hollow nanospheres (SEM images on silicon wafers) with diameters of ca. 676 nm and 661 nm are obtained in the complexes, forming 1D polymer chains. By applying a thin layer of tin(iv)corrole nanospheres to an ITO surface (AFM height images of ITO films; ∼200 nm in height), a device was fabricated with the following composition: Ag/ITO-coated glass/tin(iv)corrole nanospheres/ITO-coated glass/Ag. The resistivity (ρ) of the nanostructured film was calculated to be ∼2.4 × 10(8) Ω cm, which falls in the range of semi-insulating semiconductors. CAFM current maps at 10 V bias show bright spots with a 10-20 pA intensity and indicate that the nanospheres (∼250 nm in diameter) are the electron-conducting pathway in the device. The semi-insulating behavior arises from the non-facile electron transfer in the HOMOs of the tin(iv)corrole nanospheres.