“Axial-Bonding”-Type Hybrid Porphyrin Arrays: Synthesis, Spectroscopy, Electrochemistry, and Singlet State Properties was written by Giribabu, L.;Rao, T. Anita;Maiya, Bhaskar G.. And the article was included in Inorganic Chemistry in 1999.Electric Literature of C47H36N4O The following contents are mentioned in the article:
P(V), Ge(IV), and Sn(IV) porphyrin-based, axial-bonding-type hybrid trimers were readily constructed by employing a new building-block approach. The approach is modular in nature, and it involves simple inorganic reactions such as axial bond formation of main group element containing porphyrins and insertion of metal/metalloid ions into the porphyrin cavity. The architecture of these arrays is such that, while a P(V), Ge(IV), or Sn(IV) complex of meso-5,10,15,20-(tetratolyl)porphyrin forms the basal scaffolding unit, the free-base, vanadyl, Co(II), Ni(II), Cu(II), or Zn(II) porphyrins occupy the two axial sites via an aryloxy bridge. Synthesis of an all-P array containing three P(V) subunits also was accomplished. Each new porphyrin array studied was fully characterized by various phys. methods that include mass (FAB), UV-visible, IR, fluorescence, ESR, and 1H and 31P NMR (NMR; 1-dimensional and 2D) spectroscopies and cyclic voltammetry. The UV-visible and ESR spectral parameters and also the redox potential data suggest that there exists no interaction between the ¦Ð-planes of the constituent monomeric porphyrins in these arrays. Detailed 1H NMR studies carried out with the trimers containing diamagnetic porphyrins reveal characteristic shielding/deshielding effects for the various protons on the axial porphyrin subunits. The ground state data, as probed by the spectroscopic and electrochem. techniques, collectively indicate that there exists a sym. but nonparallel disposition of the two axial porphyrins with respect to plane of the central porphyrin. Singlet state activity of the photoactive trimers was probed by the steady state fluorescence method with selective excitation into the bands corresponding to the two constituent monomeric species. Anal. of the fluorescence emission and excitation spectral data suggests the occurrence of electronic energy transfer as well as photoinduced electron transfer reactions in trimers endowed with free-base or Zn(II) porphyrin axial subunits. Efficiencies of the excited state processes of these trimeric arrays are dependent on the type of metal/metalloid ions present in the porphyrin crevice. This study involved multiple reactions and reactants, such as 4-(10,15,20-Tri-p-tolylporphyrin-5-yl)phenol (cas: 57412-08-5Electric Literature of C47H36N4O).
4-(10,15,20-Tri-p-tolylporphyrin-5-yl)phenol (cas: 57412-08-5) belongs to catalyst ligands. The atoms and molecules used as ligands are almost always those that are capable of functioning as the electron-pair donor in the electron-pair bond (a coordinate covalent bond) formed with the metal atom. It is clear that future advancements in metal complexes and their applications crucially depend on ligand design, whereas the ligand electronic, steric and topological properties provide numerous improvements to the reactivity and selectivity at the metal centers.Electric Literature of C47H36N4O
Referemce:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI