0000000001298831
AUTHOR
Ping Chen
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…
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…
Photometric and Spectroscopic Properties of Type Ia Supernova 2018oh with Early Excess Emission from the $Kepler$ 2 Observations
Supernova (SN) 2018oh (ASASSN-18bt) is the first spectroscopically-confirmed type Ia supernova (SN Ia) observed in the $Kepler$ field. The $Kepler$ data revealed an excess emission in its early light curve, allowing to place interesting constraints on its progenitor system (Dimitriadis et al. 2018, Shappee et al. 2018b). Here, we present extensive optical, ultraviolet, and near-infrared photometry, as well as dense sampling of optical spectra, for this object. SN 2018oh is relatively normal in its photometric evolution, with a rise time of 18.3$\pm$0.3 days and $\Delta$m$_{15}(B)=0.96\pm$0.03 mag, but it seems to have bluer $B - V$ colors. We construct the "uvoir" bolometric light curve hav…
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…
Insights into the crystal packing of phosphorylporphyrins based on the topology of their intermolecular interaction energies
Four metal complexes of 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin 1M (M = Cd(II), Ni(II), Pd(II), and Pt(II)) were synthesized and crystallographically characterized. The crystal organization patterns were analyzed using DFT (B97-D3/def2-SVP) calculations of the intermolecular interaction energies between complexes in the crystals. For the systematic analysis of crystal packing, the calculations were extended to previously reported compounds 1M (M = H2, Cu(II), and Zn(II)). Quantitative analysis of the interaction energies shows the essential role of weak intermolecular interactions, such as C-H⋯O, C-H⋯π and M⋯π, in the formation of basic structural motifs and their organization …
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…
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…
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…
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…
Structural and Electrochemical Studies of Copper(I) Complexes with Diethoxyphosphoryl-1,10-phenanthrolines
Two series of copper(I) complexes with diethoxyphosphoryl-substituted 1,10-phenanthroline ligands were synthesized and characterized in the solid state and in solution. The first comprised mixed-ligand CuI complexes with phenanthroline and triphenylphosphine. The second series includes bis-chelates with two phenanthroline ligands. According to the X-ray data for the six complexes, the ditopic phenanthroline ligands exhibit bidentate coordination to the copper(I) atom through two nitrogen atoms in both series. Solution equilibria involving different phenanthroline copper(I) species were studied by 1H and 31P NMR spectroscopy, electrochemistry, and spectroelectrochemistry. The solution specia…
CCDC 902786: Experimental Crystal Structure Determination
Related Article: Anna A. Sinelshchikova, Sergey E. Nefedov, Yulia Yu. Enakieva, Yulia G. Gorbunova, Aslan Yu. Tsivadze, Karl M. Kadish, Ping Chen, Alla Bessmertnykh-Lemeune, Christine Stern, and Roger Guilard|2013|Inorg.Chem.|52|999|doi:10.1021/ic302257g
CCDC 990046: Experimental Crystal Structure Determination
Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161
CCDC 902785: Experimental Crystal Structure Determination
Related Article: Anna A. Sinelshchikova, Sergey E. Nefedov, Yulia Yu. Enakieva, Yulia G. Gorbunova, Aslan Yu. Tsivadze, Karl M. Kadish, Ping Chen, Alla Bessmertnykh-Lemeune, Christine Stern, and Roger Guilard|2013|Inorg.Chem.|52|999|doi:10.1021/ic302257g
CCDC 1502145: Experimental Crystal Structure Determination
Related Article: Jean-Michel Barbe, Benoit Habermeyer, Tony Khoury, Claude P. Gros, Philippe Richard, Ping Chen, and Karl M. Kadish|2010|Inorg.Chem.|49|8929|doi:10.1021/ic101170k
CCDC 990049: Experimental Crystal Structure Determination
Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161
CCDC 990047: Experimental Crystal Structure Determination
Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161
CCDC 902787: Experimental Crystal Structure Determination
Related Article: Anna A. Sinelshchikova, Sergey E. Nefedov, Yulia Yu. Enakieva, Yulia G. Gorbunova, Aslan Yu. Tsivadze, Karl M. Kadish, Ping Chen, Alla Bessmertnykh-Lemeune, Christine Stern, and Roger Guilard|2013|Inorg.Chem.|52|999|doi:10.1021/ic302257g
CCDC 990045: Experimental Crystal Structure Determination
Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161
CCDC 990048: Experimental Crystal Structure Determination
Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161
CCDC 990050: Experimental Crystal Structure Determination
Related Article: Alexander Mitrofanov, Machima Manowong, Yoann Rousselin, Stéphane Brandès, Roger Guilard, Alla Bessmertnykh-Lemeune, Ping Chen, Karl M. Kadish, Nataliya Goulioukina, Irina Beletskaya|2014|Eur.J.Inorg.Chem.||3370|doi:10.1002/ejic.201402161