Modified expanded corroleferrocene conjugates: syntheses, structure and properties

Chandrashekar, Tavarekere K. ; Kumar, Rajeev ; Misra, Rajneesh ; PrabhuRaja, Viswanathan (2005) Modified expanded corroleferrocene conjugates: syntheses, structure and properties Chemistry: A European Journal, 11 (19). pp. 5695-5707. ISSN 0947-6539

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Syntheses, characterization and properties of expanded corroleferrocene conjugates are reported. Ferrocenyl group are covalently linked to the corrole macrocycle through three different spacers groups. The synthetic strategy involved prior insertion of ferrocene with spacers to the dipyrromethane unit followed by a 3+2 acid-catalyzed oxidative coupling methodology. The optical and emission data of the expanded corroleferrocene conjugates depend on the nature and length of the spacer groups and the maximum effects are seen where ferrocene is directly linked to the meso carbon of macrocycle. The single crystal X-ray structure of two expanded corroleferrocene conjugates; [22]pentaphyrin ( with different meso substituents, clearly reveal shortening of the CC bond length linking the meso carbon and the aryl substituent containing the ferrocene moiety relative to meso aryl substituents without ferrocene. The results suggest that an electronic interaction between the two π systems. Electrochemical data reveal harder oxidation for the ferrocene unit in the conjugates relative to free ferrocene; this suggests the electron donating nature of the ferrocene. The first corrole ring oxidation shows easier oxidation relative to 1 and the magnitude of shifts in potential is inversely proportional to the length of spacer. The molecular first hyperpolarizabilities (β) measured at 1064 nm by HRS method vary in the range 2032×10-30 esu and imply that the β values can be increased by enhancing the number of mobile electrons in the conjugation. The conjugates form 1:1 metal complex with the RhI where rhodium is coordinated to one amino and one imino nitrogen of the dipyrromethane unit.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons, Inc.
Keywords:Corroles; Ferrocenes; Nonlinear Optics; Porphyrinoids
ID Code:5303
Deposited On:18 Oct 2010 08:33
Last Modified:27 May 2011 10:54

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