107556-84-3Relevant articles and documents
Facile synthesis of β-functionalized “push-pull” Zn(II) porphyrins for DSSC applications
Prakash, Kamal,Manchanda, Shweta,Sudhakar, Vediappan,Sharma, Nidhi,Sankar, Muniappan,Krishnamoorthy, Kothandam
, p. 56 - 66 (2017/08/08)
Three new β-substituted “push-pull” Zn(II) porphyrin dyes with various electron donors at meso-positions and cyanoacetic acid as acceptor at β-position have been designed and synthesized. These porphyrins have been characterized by UV-Vis, Fluorescence,
Structural characterization and formation kinetics of sitting-atop (SAT) complexes of some porphyrins with copper(II) ion in aqueous acetonitrile relevant to porphyrin metalation mechanism. Structures of aquacopper(II) and Cu(II)-SAT complexes as determined by XAFS spectroscopy
Inamo,Kamiya,Inada,Nomura,Funahashi
, p. 5636 - 5644 (2008/10/08)
The formation of the sitting-atop (SAT) complexes of 5,10,15,20-tetraphenylporphyrin (H2tpp), 5,10,15,20-tetrakis-(4-chlorophenyl)porphyrin (H2t(4-Clp)p), 5,10,15,20-tetramesitylporphyrin (H2tmp), and 2,3,7,8,12,13,17,18-octaethylporphyrin (H2oep) with the Cu(II) ion was spectrophotometrically confirmed in aqueous acetonitrile (AN), and the formation rates were determined as a function of the water concentration (Cw). The decrease in the conditional first-order rate constants with the increasing Cw was reproduced by taking into consideration the contribution of [Cu(H2O)(an)5]2+ in addition to [Cu(an)6]2+ to form the Cu(II)-SAT complexes. The second-order rate constants for the reaction of [Cu(an) 6]2+ and [Cu(H2O)(an)5]2+ at 298 K were respectively determined as follows: (4.1 ± 0.2) × 105 and (3.6 ± 0.2) × 104 M-1 s-1 for H2tpp, (1.15 ± 0.06) × 105 M-1 s-1 and negligible for H2t(4-Clp)p, and (4.8 ± 0.3) × 103 and (1.3 ± 0.3) × 102 M-1 s-1 for H2tmp. Since the reaction of H2oep was too fast to observe the reaction trace due to the dead time of 2 ms for the present stopped-flow technique, the rate constant was estimated to be greater than 1.5 × 106 M-1 s-1. According to the structure of the Cu(II)-SAT complexes determined by the fluorescent XAFS measurements, two pyrrolenine nitrogens of the meso-substituted porphyrins (H2tpp and H2tmp) bind to the Cu(II) ion with a Cu-N(pyr) distance of ca. 2.04 A, while those of the β-pyrrole-substituted porphyrin (H2oep) coordinate with the corresponding bond distance of 1.97 A. The shorter distance of H2oep is ascribed to the flexibility of the porphyrin ring, and the much greater rate for the formation of the Cu(II)-SAT complex of H2oep than those for the meso-substituted porphyrins is interpreted as due to a small energetic loss at the porphyrin deformation step during the formation of the Cu(II)-SAT complex. The overall formation constants, βn, of [Cu(H2O)n(an)6-n]2+ for the water addition in aqueous AN were spectrophotometrically determined at 298 K as follows: log(β1/M-1) = 1.19 ± 0.18, log(β2/M-2) = 1.86 ± 0.35, and log(β3/M-3) = 2.12 ± 0.57. The structure parameters around the Cu(II) ion in [Cu(H2O)n(an)6-n]2+ were determined using XAFS spectroscopy.
