Syntheses of quadruply two- and three-atom, aza-bridged, cofacial bis(5,10,15,20-tetraphenylporphyrins)

Photophysical Characterization of Free-Base N-Confused Tetraphenylporphyrins

“…A comparison of the relative intensities of the Q bands in H 2 -TPChl and 1i shows the ratio Q x (0,0)/Q x (1,0) to be 7.6 for H 2 -TPChl and 3.9 for 1i, which contrasts the same ratio for H 2 TPP (0.97 in CHCl 3 ). 24 The ratio Q y (0,0)/Q y (1,0) is also similar for these two compounds, where values of 0.73 (H 2 TPChl) and 0.64 (1i) are found.…”

A Biomimetic Model for the Active Site of Iron‐Only Hydrogenases Covalently Bonded to a Porphyrin Photosensitizer

“…The 1 H NMR spectrum of 3 displays a singlet at d = 4.55 ppm for the CH 2 groups in the diiron-ADT moiety and another singlet at d = À2.76 ppm for the NH groups of the porphyrin unit. [18] The electronic absorption spectra of 3 and TPP were also recorded. As shown in Figure 1, there is one Soret band at 419 nm in the near-UV region and four Q bands at 516, 552, 592, and 647 nm in the visible region.…”

The N‐Acylated Derivatives of Parent Complex [{(μ‐SCH2)2NH}Fe2(CO)6] as Active Site Models of Fe‐Only Hydrogenases: Synthesis, Characterization, and Related Properties

“…[25] In addition, the 1 H NMR spectrum of 7 exhibited one singlet at δ = 4.32 ppm and one singlet at δ = 4.11 ppm for the two protons in each of its two NCH 2 S groups, and another singlet at δ = 10.08 ppm for the proton in its formyl group, whereas 8 displayed one singlet at δ = 4.53 ppm for the two protons in each of its two NCH 2 S groups and another singlet at δ = -2.79 ppm for the protons attached to N atoms in the porphyrin moiety. [26] X-ray crystallographic analysis revealed that the structure of 7 ( Figure 4, Table 3) resembles the above-described structures of 2 and 5; compound 7 is a functionalized azadithiolate ligand that is bridged between the Fe1 and Fe2 atoms to form two fused six-membered rings: a chairshaped Fe1-S1-C8-N1-C7-S2 and a boat-shaped Fe2-S1-C8-N1-C7-S2. In addition, the N-functionality of 7, namely the carbonylbenzaldehyde group, is connected to the bridgehead N1 atom by an axial bond.…”

“…From the first band, tetraphenylporphyrin (TPPH; 0.081g, 18 %) was obtained as a purple solid, which was identified by comparison of its IR and 1 H NMR spectra with those of an authentic sample. [25,26] From the second purple band, complex 8 was obtained as a purple-red solid (0.146 g, 20 % X-ray Structure Determinations of 2, 5, and 7: Single crystals of 2, 5, and 7 suitable for X-ray diffraction analyses were grown by slow evaporation of a CH 2 Cl 2 /hexane solution of 2 or 5 at -10°C and a CH 2 Cl 2 solution of 7 at room temperature. A single crystal of 2, 5, or 7 was mounted on a Bruker SMART 1000 automated dif-296 fractometer.…”