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…
Decoupling the artificial special pair to slow down the rate of singlet energy transfer
Trimer 2, composed of a cofacial heterobismacrocycle, octamethyl-porphyrin zinc(II) and bisarylporphyrin zinc(II) held by an anthracenyl spacer, and a flanking acceptor, bisarylporphyrin free-base ( Ar = -3,5-(t Bu )2 C 6 H 3), has been studied by means of absorption spectroscopy, "steady state and time-resolved fluorescence" and fs transient absorption spectroscopy, and density functional theory (DFT) in order to assess the effect of decoupling the chromophores' low energy MOs on the rate of the singlet, S1, energy transfer, k ET , compared to a recently reported work on a heavily coupled trimeric system, Trimer 1, [biphenylenebis(n-nonyl)porphyrin zinc(II)]-bisarylporphyrin free-base ( A…
Face-to-face held Pacman type porphyrin-fullerene dyads: design, synthesis, charge transfer interactions and photophysical studies
Pacman-type face-to-face zinc-porphyrin-fullerene dyads have been newly synthesized and studied. Owing to the close proximity of the donor and acceptor entities, strong pi-pi intramolecular interactions between the porphyrin and fullerene entities resulted in modulating the spectral and electrochemical properties of the dyads. New absorption and emission bands that correspond to the charge-transfer interactions were observed in the near-IR region. Time-resolved transient absorption studies revealed efficient photoinduced electron transfer from the singlet excited porphyrin to the fullerene entity. The rate constants for photoinduced electron transfer are analyzed in terms of the Marcus theo…
Synthesis and Photodynamics of Fluorescent Blue BODIPY-Porphyrin Tweezers Linked by Triazole Rings
Novel zinc porphyrin tweezers in which two zinc porphyrins were connected with π-conjugated boron dipyrromethenes (BDP meso-Por(2) and BDP β-Por(2)) through triazole rings were synthesized to investigate the photoinduced energy transfer and electron transfer. The UV-vis spectrum of BDP β-Por(2) which has less bulky substituents than BDP meso-Por(2) exhibits splitting of the Soret band as a result of the interaction between porphyrins of BDP β-Por(2) in the excited state. Such interaction between porphyrins of both BDP β-Por(2) and BDP meso-Por(2) is dominant at room temperature, while the coordination of the nitrogen atoms of the triazole rings to the zinc ions of the porphyrins occurs at l…
Photoinduced electron transfer in supramolecular complexes of a π-extended viologen with porphyrin monomer and dimer
A π-extended viologen has been synthesized, forming supramolecular complexes with a freebase tetraphenylporphyrin (H2TPP) and the cofacial porphyrin dimer with an anthracene spacer [H4(DPA)] through π–π interaction in benzonitrile (PhCN). Formation of the H2TPP-BHV2+ supramolecular complex was probed by UV-vis and fluorescence spectra. The fluorescence of H2TPP was strongly quenched by electron transfer from the singlet excited state (1H2TPP*) to BHV2+ in the supramolecular complex. The transient absorption spectrum of the charge-separated (CS) state (H2TPP•+ and BHV•+) was successfully detected by the laser flash photolysis measurements of the H2TPP-BHV2+ supramolecular complex in PhCN. Th…
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…
Persistent electron-transfer state of a pi-complex of acridinium ion inserted between porphyrin rings of cofacial bisporphyrins
A free-base cofacial bisporphyrin, H(4)DPOx, forms a pi-complex with acridinium ion (AcH(+)) by pi-pi interaction in benzonitrile (PhCN). Formation of the H(4)DPOx-AcH(+) pi-complex was probed by UV-vis and NMR spectroscopy. The binding constant between AcH(+) and H(4)DPOx is determined as 9.7 x 10(4) M(-)(1). Photoinduced electron transfer (ET) from the H(4)DPOx to the AcH(+) moiety occurred efficiently in the pi-complex to form the ET state (H(4)DPOx(*)(+)-AcH(*)). The ET state is successfully detected by laser flash photolysis. The lifetime of the ET state is 18 mus in PhCN at 298 K, and the quantum yield of the ET state is 90%. The temperature dependence of the ET state lifetime has bee…