Homo- and Heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins: Preparation, X-ray Crystal Structure, Electronic Absorption and Emission Spectra and Density Functional Theory Calculations
MetadataShow full item record
Homo- and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M(2)10 (M(2) =H(2)/Ni, Ni(2), Ni/Zn, H(4), H(2)Zn, Zn(2)) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H(2), Ni, and ZnTriPP on the other (M(2)11), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, (1)H NMR spectra, and for the Ni(2) bis(TriPP) complex Ni(2)10, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni(II) porphyrins, and the (E)-C(2)H(2) bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H(4)10 and H(2)Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni(2)10 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV.
Showing items related by title, author, creator and subject.
Phosphotungstic acid functionalized silica nanocomposites with tunable bicontinuous mesoporous structure and superior proton conductivity and stability for fuel cellsZeng, J.; Zhou, Y.; Li, L.; Jiang, San Ping (2011)A novel proton exchange membrane using phosphotungstic acid (HPW) as proton carrier and cubic bicontinuous Ia3d mesoporous silica (meso-silica) as framework material is successfully developed as proton exchange membranes ...
Insights into Heterogeneous Catalysis of Persulfate Activation on Dimensional-Structured NanocarbonsDuan, X.; Sun, Hongqi; Kang, J.; Wang, Yuxian; Indrawirawan, S.; Wang, Shaobin (2015)A variety of dimensional-structured nanocarbons were applied for the first time as metal-free catalysts to activate persulfate (PS) for catalytic oxidation of phenolics and dyes as well as their degradation intermediates. ...
Detrital zircon record of Meso- and Neoproterozoic sedimentary basins in northern part of the Siberian Craton: Characterizing buried crust of the basementPriyatkina, N.; Khudoley, A.; Collins, William; Kuznetsov, N.; Huang, H. (2016)We present new LA ICP-MS detrital zircon data from Meso- and Neoproterozoic sedimentary basins located in the northern and western parts of the Siberian Craton. Along the western cratonic margin (Turukhansk Uplift, northern ...