Untitled

Надточенко, В. А.; Khudyakov, D. V.; Abramova, N. V.; Воронцов, Е. В.; Loim, N. M.; Гостев, Ф. Е.; Tovbin, D. G.; Titov, A. A.; Sarkisov, O. M.

doi:10.1023/a:1019657517542

Cited by 10 publications

(12 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…It was later found that the fluorescence of the porphyrin in 2 is almost completely quenched by the peripheral ferrocenyl groups. [75,76] Meso-tetrakis(4-ferrocenylphenyl)porphyrin (4) was synthesized in 15 % yield from 4-ferrocenylbenzaldehyde (3) and pyrrole using the same procedure as Hendrickson (Scheme 2). The UV/Vis spectrum is very similar to that of meso-tetraphenylporphyrin.…”

Section: Synthesis and Electronic Communicationmentioning

confidence: 99%

Merging Porphyrins with Organometallics: Synthesis and Applications

2008

View full text Add to dashboard Cite

The coordination chemistry of porphyrins has traditionally involved the ability of the porphyrin's tetrapyrrolic core to accommodate metal ions of varying charges and sizes, and on the organometallic chemistry of the resulting metalloporphyrins. However, the organometallic chemistry of porphyrins is not necessarily restricted to the metal bound in the porphyrin core, but can also be extended to the porphyrin periphery, be it through direct metalation of the porphyrin macrocycle at the meso or β position, or by attachment to or merger of the porphyrin skeleton with ligands, followed by metalation. This Review focuses on the synthetic strategies used for porphyrins with peripheral metal–carbon bonds. The exciting results that have been produced underscore the importance and future potential of this field.

show abstract

Section: Synthesis and Electronic Communicationmentioning

confidence: 99%

Merging Porphyrins with Organometallics: Synthesis and Applications

2008

View full text Add to dashboard Cite

show abstract

“…[17][18][19][20][21][22] Meso-ferrocenyl substituted porphyrins have so far received little attention, although they seem very promising in terms of their photochemical properties. [21][22][23] For instance, during our investigation of the efficient and fast electron transfer from zinc 5,10,15,20-tetraferrocenylporphyrin (ZnTFcP, strong electron donor) to 2-pyridyl-3,4-fulleropyrrolidine (electron acceptor), ZnTFcP showed interesting photoinduced electron-transfer features. 24 In 1999, Barrell et al showed a rare example of the formation of a pure atropisomer of a,a-5,15-bis(ferrocenyl)-2,8,12,18tetrabutyl-3,7,13,17-tetramethylporphyrin, which demonstrated long range (> 10 Å ) metal-metal coupling between two ferrocenyl substituents.…”

Section: Introductionmentioning

confidence: 99%

Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds

et al. 2008

View full text Add to dashboard Cite

H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] was prepared by a direct tetramerization reaction between pyrrole and ferrocene carbaldehyde in the presence of a BF(3) catalyst, while the series of MTFcP (M = Zn, Ni, Co and Cu) were prepared by a metallation reaction between H(2)TFcP and respective metal acetates. All compounds were characterized by UV-vis and MCD spectroscopy, APCI MS and MS/MS methods, high-resolution ESI MS and XPS spectroscopy. Diamagnetic compounds were additionally characterized using (1)H and (13)C NMR methods, while the presence of low-spin iron(ii) centers in the neutral compounds was confirmed by Mössbauer spectroscopy and by analysis of the XPS Fe 2p peaks, revealing equivalent Fe sites. XPS additionally showed the influence on Fe 2p binding energies exerted by the distinct central metal ions. The conformational flexibility of ferrocene substituents in H(2)TFcP and MTFcP, was confirmed using variable-temperature NMR and computational methods. Density functional theory predicts that alpha,beta,alpha,beta atropisomers with ruffled porphyrin cores represent minima on the potential energy surfaces of both H(2)TFcP and MTFcP. The degree of non-planarity is central-metal dependent and follows the trend: ZnTFcP < H(2)TFcP approximately CuTFcP < CoTFcP < NiTFcP. In all cases, a set of occupied, predominantly ferrocene-based molecular orbitals were found between the highest occupied and the lowest unoccupied, predominantly porphyrin-based molecular orbitals. The vertical excitation energies of H(2)TFcP were calculated at the TDDFT level and confirm the presence of numerous predominantly metal-to-ligand charge-transfer bands coupled via configurational interaction with expected intra-ligand pi-pi* transitions.

show abstract

“…Its photochemical and photophysical properties were studied by Nadtochenko et al [21,22] who demonstrated the ferrocene-based quenching of the porphyrin fluorescence and showed that the fluorescence quantum yield of 1H 2 is highly altered by the ferrocene groups, estimating that it is 10 5 times lower than that of the 5,10,15,20-tetrakis(phenyl)porphyrin (TPPH 2 ). The relaxation of the Q1(-*) excited state of 1H 2 and its diprotonated form 1H 4 2+ was also investigated by femtosecond laser absorption spectroscopy: the transition to the charge transfer state was shown to occur within 208 ± 10 fs for 1H 2 and 9 ± 3 ps for 1H 4 2+ .…”

Section: Direct Connectionmentioning

confidence: 99%