Self‐Assembly of Hexameric Macrocycles from PtII/Ferrocene Dimetallic Subunits – Synthesis, Characterization, Chemical Reactivity, and Oxidation Behavior. Issue 35 (9th November 2015)

• Record Type: Journal Article
• Authors: Giannetto, Antonino; Puntoriero, Fausto; Notti, Anna; Parisi, Melchiorre F.; Ielo, Ileana; Nastasi, Francesco; Bruno, Giuseppe; Campagna, Sebastiano; Lanza, Santo
• Is Part Of: European journal of inorganic chemistry. Issue 35(2015)
• Page Start: 5730
• Page End: 5742
• Publication Date: 2015-11-09
• Subjects: Self‐assembly -- Heterometallic complexes -- Macrocycles -- Metallacycles -- Platinum; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501050
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: New compoundsIa –h of the form [(Me2 SO)ClPt(HR2 DTO κ‐ S, S Pt)] (HR2 DTO = secondary dithiooxamide, with R = methyl, ethyl, n ‐propyl, n ‐butyl, n ‐decyl, isopropyl, ( R )‐1‐phenylethyl, or ( S )‐2‐hydroxypropyl; κ‐ S, S Pt denotes the coordination of the DTO moiety to the Pt atom) have been prepared and used to synthesize platinum(II)/ferrocene dimetallic speciesIIa –h of formula [(dppf)Pt(HR2 DTO κ‐ S, S Pt)]Cl (dppf = 1, 1′‐diphosphinoferrocene). ComplexesIIa –e, bearing unbranched groups on the dithiooxamide moiety (i.e., R = methyl, ethyl, n ‐propyl, n ‐butyl, or n ‐decyl groups), self‐assemble upon standing to form unprecedented hexameric macrocyclesIIIa –e . CompoundsIIa –e, IIIa –e, as well asIIf –h, have been characterized by a combination of 1 H, 13 C, 31 P NMR spectroscopy and 2D‐ROESY and diffusion‐ordered NMR spectroscopy (DOSY) experiments; the latter experiments have been used to calculate the hydrodynamic radius ofIIa –e andIIIa –e, assisted by the data provided by the X‐ray crystal structure ofIIh . CompoundsIIIa –e are characterized by the presence of six dppf bridging units occupying the inner rim of the macrocycles and exhibit interesting properties, for example, oxidation ofIIIa –e occurs around +0.40 V versus saturated calomel electrode (SCE), whereas oxidation of the typeII species occurs at potentials greater than +1.0 V. Oxidation ofIIIa –e is explained through a delocalized orbital extending over the six dppf subunits. The reversibility of the self‐assembly process is finally demonstrated by alternate addition of acids and bases to the typeIII compounds. Abstract : Dimetallic building blocks containing Pt II dithiooxamide and ferrocene subunits self‐assemble in solution to generate unprecedented hexameric macrocycles that have peculiar geometrical, spectroscopic, redox, and reactivity properties. The self‐assembly process is reversible and can be repeated at will by alternating suitable inputs.