Synthesis and Characterization of Dirhodium(II,II)−Porphyrin-Based Multiredox Systems
2002; Wiley; Volume: 2002; Issue: 1 Linguagem: Inglês
10.1002/1099-0682(20021)2002
ISSN1099-0682
AutoresSandra Lo Schiavo, Scolastica Serroni, Fausto Puntoriero, Giuseppe Tresoldí, Pasquale Piraino,
Tópico(s)Magnetism in coordination complexes
ResumoEuropean Journal of Inorganic ChemistryVolume 2002, Issue 1 p. 79-86 Full Paper Synthesis and Characterization of Dirhodium(II,II)−Porphyrin-Based Multiredox Systems Sandra Lo Schiavo, Sandra Lo Schiavo [email protected] Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorScolastica Serroni, Scolastica Serroni Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorFausto Puntoriero, Fausto Puntoriero Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorGiuseppe Tresoldi, Giuseppe Tresoldi Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorPasquale Piraino, Pasquale Piraino Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this author Sandra Lo Schiavo, Sandra Lo Schiavo [email protected] Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorScolastica Serroni, Scolastica Serroni Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorFausto Puntoriero, Fausto Puntoriero Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorGiuseppe Tresoldi, Giuseppe Tresoldi Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this authorPasquale Piraino, Pasquale Piraino Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone n. 31, 98166 Vil. S. Agata, Messina, ItalySearch for more papers by this author First published: 29 November 2001 https://doi.org/10.1002/1099-0682(20021)2002:1 3.0.CO;2-2Citations: 21Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Dirhodium(II,II)−porphyrin-based multiredox systems were easily prepared by combining the versatile reactivity, both axial and equatorial, of the [Rh2(form)2(O2CCF3)2(H2O)2] (form = N,N′-di-p-tolylformamidinate) complex and the well-known coordination capability of meso-substituted phenylporphyrins. In this way, redox systems featured by porphyrins axially or equatorially coordinated to the dirhodium subunits were obtained. Electrochemical and luminescence properties of the new assemblies were also investigated. Porphyrin−dirhodium(II,II) multiredox assemblies were synthesized by exploiting both the classical axial and the peculiar equatorial reactivity of the complex [Rh2(form)2(O2CCF3)2(H2O)2] (1) (form = N,N′-di-p-tolylformamidinate). The species [Rh2(form)2(PCOO)2] (2), featuring two bridged (carboxyphenyl)porphyrins in the equatorial positions, was prepared by metathetical reaction of 1 with the sodium salt of meso-5-(4-carboxyphenyl)-5,10,15-triphenylporphyrin (PCOO). Conversely, redox systems in which porphyrins are axially ligated to dirhodium were obtained by treating 1 with a variety of functionalized meso-pyridylporphyrins. Depending on the number and position of the peripheral pyridyl substituents, assemblies with different nuclearity, both in terms of metal and porphyrin subunits, were isolated. The 1:2 dirhodium/porphyrin adduct, [Rh2(form)2(O2CCF3)2(PyP)2] (3) was obtained by treatment of 1 with triphenyl(pyridyl)porphyrin (PyP). By combination of 1 with the cis-5,10-diphenyl-15,20-dipyridylporphyrin (cis-DPyP) the molecular square box, [Rh2(form)2(CF3CO2)2(cis-DPyP)]4 (4) was isolated in good yield. The reaction of 1 with 5,10,15,20-tetrakis(4-pyridyl)porphyrin (TPyP) is dependent on the experimental conditions and led to two different products: the grid polymer [{Rh2(form)2(CF3CO2)2}2(TPyP)]n (5) and the symmetric tetramer [{Rh2(form)2(CF3CO2)2}4(TPyP)] (6), respectively. All the products were characterized by conventional spectroscopic methods. Proton NMR spectroscopy resulted particularly useful for the characterization of dirhodium− phenyl(pyridyl)porphyrin aggregates. The 2,6-pyridyl proton resonances are highly affected by coordination and experience significantly upfield shifts with respect to the corresponding unbound porphyrin. Systems 2, 3, 4, and 6 underwent many redox processes in the potential window under investigation (+2; −1.4 V), each one of them can be assigned to the specific subunits of the molecular arrays. 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