Substitution pattern in ruthenium octa-n-butoxyphthalocyanine complexes influence their reactivity in N–H carbene insertions

The ability of P(V) phthalocyanines (Pcs) for efficient singlet oxygen (SO) generation was demonstrated for the first time by the example of unsubstituted and α- and β-octabutoxy-substituted P(V)Pcs with hydroxy, methoxy and phenoxy ligands in the apical positions of the octahedral P centre. Variation of substituents in Pc ring and P(V) axial ligands allows careful tuning of photophysical and photochemical properties. Indeed, a combination of BuO groups in the β-positions of the Pc ring and PhO groups as axial ligands provides significant SO generation quantum yields up to 90%; meanwhile, the values of SO generation quantum yields for others investigated compounds vary from 27 to 55%. All the complexes, except α-substituted P(V)Pc, demonstrate fluorescence with moderate quantum yields (10–16%). The introduction of electron-donating butoxy groups, especially in the α-position, increases the photostability of P(V)Pcs. Moreover, it has been shown in the example of β-BuO-substituted P(V) that the photostability depends on the nature of axial ligands and increases in the next row: OPh < OMe < OH. The presence of oxy/hydroxy axial ligands on the P(V) atom makes it possible to switch the photochemical and photophysical properties of P(V)Pcs by changing the acidity of the media.

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“…1,4,8,11,15,18,22,25-Octabutoxyphthalocyanine ( 3 ) was prepared from 3,6-dibutyloxy-1,2-dicyanobenzene according to the literature [ 34 , 35 ].…”

Section: Methodsmentioning

confidence: 99%

Tuning Photochemical and Photophysical Properties of P(V) Phthalocyanines

et al. 2023

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Formal Insertion of a Metal Carbene Complex into a σ‐Carbon‐Carbon Bond. Gold‐Catalyzed Synthesis of 3H‐Indoles

Allegue,

Sampedro,

Ballesteros

et al. 2024

Adv Synth Catal

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We report here a formal insertion of a metal carbene complex in a single carbon‐carbon bond. This behavior occurs with the participation of an alpha‐imino gold carbene complex, generated from benzofused triazapentalenes or, in a one‐pot procedure, from their 1‐propargyl‐1H‐bentrotriazole precursors, and gold‐catalytically activated ynamides. As the result, 3H‐indole derivatives were obtained, with formation of a quaternary center. A computational analysis carried out on the reaction mechanism indicates that the bulkiness of the gold ligand plays a key role forcing a conformation, which includes aromatic interactions, that favors the approximation of the carbenic carbon to the reactive site. In addition, a negative crossover experiment rules out a cationic arene migration pathway.

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Tetraquinoxalinoporphyrazine – π-extended NIR-absorbing photosensitizer with improved photostability

et al. 2023

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Substitution pattern in ruthenium octa-n-butoxyphthalocyanine complexes influence their reactivity in N–H carbene insertions

Abstract: Ruthenium phthalocyanine complexes bearing n-OBu substituents in the peripheral or non-peripheral positions are efficient catalysts for the selective double or single carbene insertion to the amine N-H bonds. This complementary...

Cited by 5 publications

References 45 publications

Tuning Photochemical and Photophysical Properties of P(V) Phthalocyanines

Tuning Photochemical and Photophysical Properties of P(V) Phthalocyanines

Formal Insertion of a Metal Carbene Complex into a σ‐Carbon‐Carbon Bond. Gold‐Catalyzed Synthesis of 3H‐Indoles

Tetraquinoxalinoporphyrazine – π-extended NIR-absorbing photosensitizer with improved photostability

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