Macrocyclic complexes of [Ru(N-N)(2)](2+) units [N-N=1,10 phenanthroline or 4-(p-anisyl)-1,10-phenanthroline]: Synthesis and photochemical expulsion studies (Articolo in rivista)

Type
Label
  • Macrocyclic complexes of [Ru(N-N)(2)](2+) units [N-N=1,10 phenanthroline or 4-(p-anisyl)-1,10-phenanthroline]: Synthesis and photochemical expulsion studies (Articolo in rivista) (literal)
Anno
  • 2003-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1002/ejic.200390066 (literal)
Alternative label
  • Laemmel, A. C.; Collin, J. P.; Sauvage, J. P.; Accorsi, G.; Armaroli, N. (2003)
    Macrocyclic complexes of [Ru(N-N)(2)](2+) units [N-N=1,10 phenanthroline or 4-(p-anisyl)-1,10-phenanthroline]: Synthesis and photochemical expulsion studies
    in European journal of inorganic chemistry (Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Laemmel, A. C.; Collin, J. P.; Sauvage, J. P.; Accorsi, G.; Armaroli, N. (literal)
Pagina inizio
  • 467 (literal)
Pagina fine
  • 474 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • ISOF - Istituto per la sintesi organica e la fotoreattività (literal)
Titolo
  • Macrocyclic complexes of [Ru(N-N)(2)](2+) units [N-N=1,10 phenanthroline or 4-(p-anisyl)-1,10-phenanthroline]: Synthesis and photochemical expulsion studies (literal)
Abstract
  • Two ruthenium complexes [Ru(phen)(2)(m-36)](2+) and [Ru(aphen)2(m-36) 121, indicated as 1 and 2 respectively, which contain a 36-membered macrocycle incorporating a sterically hindered bipyridine (m-36), and two 1,10-phenanthroline (phen) or 4-(P-anisyl)-1,10-phenanthroline (aphen) ligands, have been synthesised. Under light irradiation, as seen from the metal- to-ligand-charge-transfer (MLCT) bands of the visible spectral region, the [Ru(phen)12 2+ core of I and 2 is selectively expelled from the macrocycle to give the corresponding bis- acetonitrile derivative. This photochemical process was found to be notably less efficient than that observed in a simpler related complex [Ru(phen)(2)dmbp](2+) (dmbp = 6,6'dimethyl- 2,2'-bipyridine), that lacks the macrocyclic motif. In the case of I thermal back reaction takes place quantitatively affording a completely reversible system. The isolation, by chromatographic techniques, of the axial-axial cis- [(a,a)Ru(dphen)(2)Cl-2] isomer, where the two aphen ligands bear two p-anisyl groups disposed trans to one another enabled the preparation of 2. This type of complex undergoes a more complicated photochemical process, in fact, following the expected photolabilisation of the [Ru(aphen)(2)](2+) unit, photoisomerisation of the primary photo-product occurs and gives a statistical mixture of the three geometrical isomers: cis-[(a, a)Ru(aphen)(2)(CH3CN)(2)] (PF6)(2), cis-[ (a, e)Ru(aphen)(2)(CH3CN)(2)](PF6)(2) and cis-[ (e,e)Ru(aphen)(2)(CH3CN)(2)](PF6)(2) This side-reaction precludes its use as rotaxane precursor suggesting that, for this purpose, a bis-phenanthroline ligand stabilising the ruthenium core is needed. (literal)
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