71763-49-0Relevant academic research and scientific papers
Synthesis, spectral and redox properties of closely spaced pyrrole-β-position-linked porphyrin-fullerene dyads
Wu, Zhen-Yi,Yang, Sheng-Yan
, p. 244 - 254 (2019/04/17)
Two free base meso-tetraphenylporphyrin-fullerene dyads, H2PMe-C60, H2POMe-C60, and their zinc complexes, ZnPMe-C60 and ZnPOMe-C60, which the para positions of the meso-tetrasubstituted phenyl groups of the porphyrin core were substituted by methyl(-Me) and methoxyl(-OMe) groups respectively, were synthesized. The porphyrin unit in the synthesized dyads is directly linked to the fullerene entity through the pyrrole-β- position rather than through the traditionally meso-substituted phenyl group, which may be more favorable for electron communication between the donor and the acceptor. They are fully characterized by mass spectrometry, nuclear magnetic resonance, infrared spectroscopy and ultraviolet visible spectroscopy. Experimental results obtained from steady-state fluorescence spectroscopy and cyclic voltammetry show that the coordination of the zinc ions lead to an increase in the singlet excited state energy of the metallated porphyrin unit by about 0.15 eV, and to a reduce in the HOMO level and in the HOMO-LUMO energy gap. The molecular reorganization energy decreases after the electron-donating groups of -Me or -OMe attaching to the para position of the meso-phenyl group of the porphyrin moiety. The results of the energy calculations show that photoinduced electron transfer is thermodynamically favorable for the synthesized porphyrin-C60 dyads. There exists a competition between the photoinduced electron transfer and energy transfer processes from the first singlet excited state of porphyrin core to fullerene moiety. The photoinduced electron transfer rate constant of the dyads were calculated according to Marcus theory. The results indicate that the coordination of metal zinc ions lead to great increase in the electron transfer rate constant. Further, the photoinduced electron transfer rate constant increases in the order ZnP-C60, ZnPMe-C60, ZnPOMe-C60.
Synthesis and Photophysical Properties of Porphyrin–Arylimidazole Heterodyads
Zheng, Wei,Li, Xianglin,Chen, Hongbiao,Xie, Qiong,Li, Huaming
, p. 1522 - 1528 (2017/03/27)
A series of directly linked metalloporphyrin–arylimidazole heterodyads (3, 4, and 6) with an arylimidazole unit at the meso- or β-pyrrolic position of the porphyrin were synthesized via Debus–Radziszewsk reaction. Introduction of a copper ion into the porphyrin contributed significantly to the overall stability of the heterodyads. The absorption spectra indicated that the basic electronic characteristics of both individual units (i.e., metalloporphyrin and arylimidazole) were retained in the heterodyads. In addition, strong fluorescence quenching was observed in the case of the heterodyads containing copper(II) porphyrin. Cyclic voltammetric studies revealed that the heterodyads were more difficult to oxidize compared with the pristine metalloporphyrins.
Mono- and tri-β-substituted unsymmetrical metalloporphyrins: synthesis, structural, spectral and electrochemical properties
Prakash, Kamal,Kumar, Ravi,Sankar, Muniappan
, p. 66824 - 66832 (2015/08/24)
Mono-/tri-β-substituted metalloporphyrins, viz. MTPP(X)Y2 (X = CHO, CH2OH, COOH; Y = H, Br, Ph; M = 2H, Co(ii), Ni(ii), Cu(ii), Zn(ii)) have been synthesized and characterized. This work examines the influence of β-substitution on the structural, spectral and electrochemical redox properties of MTPP(X) and MTPP(CHO)Y2. The redox tunability was achieved by introducing electron donors (CH2OH and Ph) and acceptors (CHO, COOH and Br) on the MTPP skeleton. Dramatic reduction in the HOMO-LUMO gap with considerable increment in Δa1u was observed as the number of electron withdrawing groups increased. The spectral and electrochemical redox potentials are influenced by the peripheral β-substituents and electronegativity of the core metal ion. These porphyrins exhibited tunable electronic spectral and redox properties with modulated frontier orbitals by means of mono- and tri-β-substituents which are in direct conjugation with the porphyrin π-system. DFT studies of these porphyrins revealed that mono-substituted porphyrins are nearly planar whereas tri-substituted porphyrins have a moderate nonplanar conformation.
Reductive Amination-A convenient method for generating diverse, mono-functionalised 5,10,15,20-tetraphenyl porphyrins
Welch, Chris,Archibald, Stephen J.,Boyle, Ross W.
scheme or table, p. 551 - 556 (2009/08/07)
Formylation followed by reductive amination of 5,10,15,20-tetraphenyl porphyrin (TPP) is shown to be a versatile synthetic procedure for monosubstitution of the porphyrin core re-giospecifically at one β-position. A diverse range of substituents can be introduced in this way in good yields, including cyclen aza-crown macrocycles. Georg Thieme Verlag Stuttgart.
Synthesis and reactivity of metal-containing monomers 64. Synthesis, structure, polymerization, and catalytic properties of the palladium and cobalt vinylporphyrin complexes
Berezovskii,Woehrle,Tsaryova,Makarov,Pomogailo,Glagolev,Zhilina,Voloshanovskii,Roshchupkin,Pomogailo
, p. 160 - 167 (2008/02/12)
2-Vinylporphyrin and its complexes with PdII and CoII were synthesized and characterized by NMR, IR, and mass spectra. The palladium vinylporphyrin complexes are efficient metal-containing monomers in radical copolymerization with styrene. Palladium(II) in an amount of up to 1 mol.% can thus be introduced into the polymers. The synthesized polymeric Pd complexes perform the photosynthesized activation of dioxygen to the lowest excited singlet state, which is an active oxidizing agent for anthracene producing the 1,4-addition products. The monomeric and macromolecular cobalt complexes are chain-transfer catalysts in radical styrene polymerization. Springer Science+Business Media, Inc. 2007.
Syntheses and optical and electrochemical properties of porphyrin dimers linked by metal ions
Richeter, Sebastien,Jeandon, Christophe,Gisselbrecht, Jean-Paul,Ruppert, Romain,Callot, Henry J.
, p. 6168 - 6179 (2007/10/03)
The preparation, isolation, and characterization of several new peripherally functionalized monomeric porphyrins and metalloporphyrins and of porphyrin dimers are described. These dimers are obtained by linking with metal ions two monomeric porphyrins bearing at their periphery an enaminoketone chelate fully conjugated with the aromatic ring. Porphyrin dimers linked by metal ions display large interactions in the ground state as evidenced by their electronic spectra and their electrochemical behavior. Compared to the monomeric analogue, these dimers show absorption spectra with intensified red-shifted Q-bands and their first oxidation potentials are substantially lowered and split into two distinct redox steps.
