Phenothiazin-Derivate II. 1,3,6-Trisubstituierte und 1,3,6,8-tetrasubstituierte Phenothiazin-Derivate

Dye-Sensitized Solar Cell Studies of a Donor-Appended Bis(2,9-dimethyl-1,10-phenanthroline) Cu(I) Dye Paired with a Cobalt-Based Mediator

“…2,4,6,8-Tetramethyl-10 H -phenothiazine (TMPTZ) was prepared as previously reported from bis(3,5-dimethylphenyl)amine . A sample of TMPTZ (0.1048 g, 0.41 mmol) was placed in a 6 dram vial, capped with a rubber septum, and purged with N 2 (g).…”

“…2,4,6,8-Tetramethyl-10H-phenothiazine (TMPTZ) was prepared as previously reported from bis(3,5-dimethylphenyl)amine. 27 A sample of TMPTZ (0.1048 g, 0.41 mmol) was placed in a 6 dram vial, capped with a rubber septum, and purged with N 2 (g). Separately, KN[Si(CH 3 ) 3 ] 2 (0.0714 g, 0.36 mmol) was dissolved in 10 mL of THF under N 2 (g) and then injected into the vial containing the TMPTZ.…”

Photoinduced Multistep Charge Separation in a Heteroleptic Cu(I) Bis(phenanthroline)-Based Donor–Chromophore–Acceptor Triad

“…Also, the four methyl groups on each PTZ moiety were incorporated to shift the redox potential of the parent PTZ to a sufficiently negative value that it can be oxidized by [Cu(II)P 2 ] 2+ . 48 Finally, it was initially thought that the steric effect of having bulky donors located at the 2-and 9-positions might favor the equilibrium formation of the desired heteroleptic complex (e.g., as opposed to the homoleptic bis-donor complex). 34,49,50 On the basis of 1 24 Unfortunately, the UV−vis spectrum of the oxidized donor and reduced acceptor strongly overlap.…”

“…Molecular models indicated that in a D 2 d coordination geometry, attaching the donors to the methyl substituents at the 2- and 9-positions would facilitate the desired facile π-stacking with the second phenanthroline ligand. Also, the four methyl groups on each PTZ moiety were incorporated to shift the redox potential of the parent PTZ to a sufficiently negative value that it can be oxidized by [Cu(II)P 2 ] 2+ . Finally, it was initially thought that the steric effect of having bulky donors located at the 2- and 9-positions might favor the equilibrium formation of the desired heteroleptic complex (e.g., as opposed to the homoleptic bis-donor complex). ,, On the basis of 1 H NMR studies, this latter hypothesis has some limited merit in more polar solvents; however, in the relatively nonpolar solvent employed in this study, o -difluorobenzene ( o -DFB), a sample containing 1:1:1 stoichiometry of L-D, L-A, and [Cu(AN) 4 ]BF 4 (AN = acetonitrile) resulted in the assembly of all of the Cu(I) into the three complexes [Cu(L-A) 2 ] 9+ , [Cu(L-D)(L-A) 2 ] 5+ , and [Cu(L-D) 2 ] + in essentially statistical amounts (i.e., 1:2:1; see the 1 H NMR data in the Supporting Information).…”