Synthesis and characterization of homo- and heteroporphyrin dimers involving a rhodium-indium bond

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

“…Moreover, an efficient photoinduced homolytic bond cleavage of the M‐M′ bond is observed at room temperature. This phenomenon is also well known for parent compounds of the type Rh(Por)‐In(Por′) (Por=Por′ and Por′Por′; Por=Por′= TPP, OEP) (19–21). This process occurs at the ps timescale (21).…”

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

“…Moreover, an efficient photoinduced homolytic bond cleavage of the M‐M′ bond is observed at room temperature. This phenomenon is also well known for parent compounds of the type Rh(Por)‐In(Por′) (Por=Por′ and Por′Por′; Por=Por′= TPP, OEP) (19–21). This process occurs at the ps timescale (21).…”

Photogeneration of Monomeric Porphyrins from the (tetraphenylporphyrin)Rh−In(octaethylporphyrin) Dissociation of the Rh−In Bond: Investigation of Their Reactions in the Picosecond−Microsecond Time Domain

“…Inspection of the transient spectra, Figure , reveals that prompt flash-generated optical absorptions at 600 nm are, in relation to those at 440 nm, much larger than can be expected for the lowest excited state of the porphyrins. − Also the assignment of such spectra to the lowest excited state provides a dubious rationale for the lack of a perceptible luminescence. On the basis of the observed reaction with CH 2 Cl 2 , Figure , and reported products from steady-state photolysis, , these primary species are most likely the result of a homolytic dissociation of the Rh−In bond. Spectral transformations with a rate constant k = 4.1 × 10 10 M -1 s -1 , Figure , indicate that the primary products undergo transformations that lead to intermediates which are scavenged by CH 2 Cl 2 on a longer time scale, Figure .…”

“…Materials. The metal−metal-bonded complexes were available from previous work and were used without further purification. , The solvents, toluene and dichloromethane, were Aldrich HPLC grade and used without further purification.…”

Spectroscopic and Structural Study of Metal−Metal Bonded Metalloporphyrinic Derivatives: the Case of Rhodium−Indium

“…In Table , we observe that in the series [(OEP)RhIn(Porph)] the [(TPyP)In-] unit does not change the λ max of the Soret band relative to the bimetallic complex [(OEP)RhIn(TPP)] (370 nm) 27b. The saddle-shape distortion of octahalogenated porphyrin is expected to influence the distance of the two rings and the nature of π − π interactions.…”

“…In the case of [(TPP)RhIn(Porph)] series, the [(TPyP)In-] moiety has no effect on the Soret band related to the complex [(TPP)RhIn(TPP)] (416 nm),27b but the λ max of the Soret band in β - tetra and β - octa halogenated porphyrinic derivatives is gradually blue-shifted: a 23 nm difference in [(TPP)RhIn(β - Cl 8 TPP)] and a 31 nm difference in [TPP)RhIn(β - Cl 4 TPP)]. In the Β band region for the meso-substituted porphyrins, the higher-intensity B band is observed at 417 nm and the lower-intensity B band is blue-shifted (379 nm) ).…”

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

“…Moreover, an efficient photoinduced homolytic bond cleavage of the M‐M′ bond is observed at room temperature. This phenomenon is also well known for parent compounds of the type Rh(Por)‐In(Por′) (Por=Por′ and Por′Por′; Por=Por′= TPP, OEP) (19–21). This process occurs at the ps timescale (21).…”

Photogeneration of Monomeric Porphyrins from the (tetraphenylporphyrin)Rh−In(octaethylporphyrin) Dissociation of the Rh−In Bond: Investigation of Their Reactions in the Picosecond−Microsecond Time Domain

“…Inspection of the transient spectra, Figure , reveals that prompt flash-generated optical absorptions at 600 nm are, in relation to those at 440 nm, much larger than can be expected for the lowest excited state of the porphyrins. − Also the assignment of such spectra to the lowest excited state provides a dubious rationale for the lack of a perceptible luminescence. On the basis of the observed reaction with CH 2 Cl 2 , Figure , and reported products from steady-state photolysis, , these primary species are most likely the result of a homolytic dissociation of the Rh−In bond. Spectral transformations with a rate constant k = 4.1 × 10 10 M -1 s -1 , Figure , indicate that the primary products undergo transformations that lead to intermediates which are scavenged by CH 2 Cl 2 on a longer time scale, Figure .…”

“…Materials. The metal−metal-bonded complexes were available from previous work and were used without further purification. , The solvents, toluene and dichloromethane, were Aldrich HPLC grade and used without further purification.…”

Spectroscopic and Structural Study of Metal−Metal Bonded Metalloporphyrinic Derivatives: the Case of Rhodium−Indium

“…In Table , we observe that in the series [(OEP)RhIn(Porph)] the [(TPyP)In-] unit does not change the λ max of the Soret band relative to the bimetallic complex [(OEP)RhIn(TPP)] (370 nm) 27b. The saddle-shape distortion of octahalogenated porphyrin is expected to influence the distance of the two rings and the nature of π − π interactions.…”

“…In the case of [(TPP)RhIn(Porph)] series, the [(TPyP)In-] moiety has no effect on the Soret band related to the complex [(TPP)RhIn(TPP)] (416 nm),27b but the λ max of the Soret band in β - tetra and β - octa halogenated porphyrinic derivatives is gradually blue-shifted: a 23 nm difference in [(TPP)RhIn(β - Cl 8 TPP)] and a 31 nm difference in [TPP)RhIn(β - Cl 4 TPP)]. In the Β band region for the meso-substituted porphyrins, the higher-intensity B band is observed at 417 nm and the lower-intensity B band is blue-shifted (379 nm) ).…”

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

“…Moreover, an efficient photoinduced homolytic bond cleavage of the M‐M′ bond is observed at room temperature. This phenomenon is also well known for parent compounds of the type Rh(Por)‐In(Por′) (Por=Por′ and Por′Por′; Por=Por′= TPP, OEP) (19–21). This process occurs at the ps timescale (21).…”

Photogeneration of Monomeric Porphyrins from the (tetraphenylporphyrin)Rh−In(octaethylporphyrin) Dissociation of the Rh−In Bond: Investigation of Their Reactions in the Picosecond−Microsecond Time Domain

“…Inspection of the transient spectra, Figure , reveals that prompt flash-generated optical absorptions at 600 nm are, in relation to those at 440 nm, much larger than can be expected for the lowest excited state of the porphyrins. − Also the assignment of such spectra to the lowest excited state provides a dubious rationale for the lack of a perceptible luminescence. On the basis of the observed reaction with CH 2 Cl 2 , Figure , and reported products from steady-state photolysis, , these primary species are most likely the result of a homolytic dissociation of the Rh−In bond. Spectral transformations with a rate constant k = 4.1 × 10 10 M -1 s -1 , Figure , indicate that the primary products undergo transformations that lead to intermediates which are scavenged by CH 2 Cl 2 on a longer time scale, Figure .…”

“…Materials. The metal−metal-bonded complexes were available from previous work and were used without further purification. , The solvents, toluene and dichloromethane, were Aldrich HPLC grade and used without further purification.…”

Spectroscopic and Structural Study of Metal−Metal Bonded Metalloporphyrinic Derivatives: the Case of Rhodium−Indium

“…In Table , we observe that in the series [(OEP)RhIn(Porph)] the [(TPyP)In-] unit does not change the λ max of the Soret band relative to the bimetallic complex [(OEP)RhIn(TPP)] (370 nm) 27b. The saddle-shape distortion of octahalogenated porphyrin is expected to influence the distance of the two rings and the nature of π − π interactions.…”

“…In the case of [(TPP)RhIn(Porph)] series, the [(TPyP)In-] moiety has no effect on the Soret band related to the complex [(TPP)RhIn(TPP)] (416 nm),27b but the λ max of the Soret band in β - tetra and β - octa halogenated porphyrinic derivatives is gradually blue-shifted: a 23 nm difference in [(TPP)RhIn(β - Cl 8 TPP)] and a 31 nm difference in [TPP)RhIn(β - Cl 4 TPP)]. In the Β band region for the meso-substituted porphyrins, the higher-intensity B band is observed at 417 nm and the lower-intensity B band is blue-shifted (379 nm) ).…”