“…In this work, we report the photophysical and photochemical properties of such models of electron donor and acceptor systems. The preliminary communications have been reported elsewhere. , 1 2 …”
Section: Introductionmentioning
confidence: 96%
“…The preliminary communications have been reported elsewhere. 14,15 Results and Discussion Absorption Spectral Properties. Absorption spectra of viologen-linked diads and their metal complexes in MeCN are shown in Figures S1 and S2, and their numerical data are shown in Tables S1 and S2.…”
Section: Introductionmentioning
confidence: 99%
“…Therefore, the excited singlet state after irradiation by light is expected to have two conformers corresponding to an extended and perpendicular form and a closed one, in the latter of which the viologen moiety is close to the porphyrin plane. The second model is a new type of viologen-bridged diad (14,Chart 2) to construct the orthogonal orientation between porphyrin and viologen by restricting the free rotation of the viologen unit. By inserting metal ions into the N-alkylporphyrin diads, the extended conformer must exist predominantly in solution due to charge repulsion between a central metal ion and the viologen moiety.…”
A new type of viologen-linked or -bridged N-alkylporphyrin and metalloporphyrin diads was synthesized and characterized by 1 H NMR spectroscopy. Although the viologen moiety of free base diads linked with a methylene chain is flexible in solution, the insertion of metal ions results in the extended conformation, where the viologen moiety is located nearly perpendicular to the N-alkylporphyrin plane. The diad, having two porphyrin units bridged by a viologen moiety, is more rigid in conformation than the diad containing one porphyrin unit. The fluorescence quantum yields in the viologen-linked and -bridged N-alkylporphyrins become larger by insertion of H + , Mg 2+ , Al 3+ , and Si 4+ into the N-alkylporphyrins. This may arise because the extended and orthogonal conformer due to the electrostatic repulsion between the viologen and the central metal ion decelerates the ET quenching of N-alkylporphyrin by the bound viologen unit.
“…In this work, we report the photophysical and photochemical properties of such models of electron donor and acceptor systems. The preliminary communications have been reported elsewhere. , 1 2 …”
Section: Introductionmentioning
confidence: 96%
“…The preliminary communications have been reported elsewhere. 14,15 Results and Discussion Absorption Spectral Properties. Absorption spectra of viologen-linked diads and their metal complexes in MeCN are shown in Figures S1 and S2, and their numerical data are shown in Tables S1 and S2.…”
Section: Introductionmentioning
confidence: 99%
“…Therefore, the excited singlet state after irradiation by light is expected to have two conformers corresponding to an extended and perpendicular form and a closed one, in the latter of which the viologen moiety is close to the porphyrin plane. The second model is a new type of viologen-bridged diad (14,Chart 2) to construct the orthogonal orientation between porphyrin and viologen by restricting the free rotation of the viologen unit. By inserting metal ions into the N-alkylporphyrin diads, the extended conformer must exist predominantly in solution due to charge repulsion between a central metal ion and the viologen moiety.…”
A new type of viologen-linked or -bridged N-alkylporphyrin and metalloporphyrin diads was synthesized and characterized by 1 H NMR spectroscopy. Although the viologen moiety of free base diads linked with a methylene chain is flexible in solution, the insertion of metal ions results in the extended conformation, where the viologen moiety is located nearly perpendicular to the N-alkylporphyrin plane. The diad, having two porphyrin units bridged by a viologen moiety, is more rigid in conformation than the diad containing one porphyrin unit. The fluorescence quantum yields in the viologen-linked and -bridged N-alkylporphyrins become larger by insertion of H + , Mg 2+ , Al 3+ , and Si 4+ into the N-alkylporphyrins. This may arise because the extended and orthogonal conformer due to the electrostatic repulsion between the viologen and the central metal ion decelerates the ET quenching of N-alkylporphyrin by the bound viologen unit.
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