Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes. Issue 40 (3rd October 2017)

• Record Type: Journal Article
• Authors: Ferrer, Montserrat; Giménez, Leticia; Gutiérrez, Albert; Lima, João Carlos; Martínez, Manuel; Rodríguez, Laura; Martín, Avelino; Puttreddy, Rakesh; Rissanen, Kari
• Is Part Of: Dalton transactions. Volume 46:Issue 40(2017)
• Page Start: 13920
• Page End: 13934
• Publication Date: 2017-10-03
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt02732j
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The synthesis of photophysical active polytopic alkynyl gold(i ) metallaligands and preliminary studies of their interaction with metal cations are presented. Abstract : A series of alkynyl gold(i ) tri and tetratopic metallaligands of the type [Au3 (CC–R)3 (μ3 -triphosphane)] (R = 2, 2′-bipyridin-5-yl or C10 H7 N2, 2, 2′:6′, 2′′-terpyridin-4-yl or C15 H10 N3 ; triphosphane = 1, 1, 1-tris(diphenylphosphanyl)ethane or triphos, 1, 3, 5-tris(diphenylphosphanyl)benzene or triphosph) and [Au4 (CC–R)4 (μ4 -tetraphosphane)] (R = C10 H7 N2, C15 H10 N3 ; tetraphosphane = tetrakis(diphenylphosphanylmethyl)methane or tetraphos, 1, 2, 3, 5-tetrakis(diphenylphosphanyl)benzene or tpbz, tetrakis(diphenylphosphaneylmethyl)-1, 2-ethylenediamine or dppeda) were obtained in moderate to good yields. All complexes could be prepared by a reaction between the alkynyl gold(i ) polymeric species [Au(CC–R)] n and the appropriate polyphosphane. An alternative strategy that required the previous synthesis of the appropriate acetylacetonate precursors [Au n (acac) n (μ n -polyphosphane)] ("acac method") was assayed, nevertheless only the polyacac derivatives [Au3 (acac)3 (μ3 -triphosphane)] (triphosphane = triphos and triphosph) and [Au4 (acac)4 (μ4 -tetraphos)] could be isolated and characterized. All compounds were characterized by IR, multinuclear NMR spectroscopy and ESI(+) mass spectrometry. The X-ray crystal structure of complexes [Au4 (CC–C10 H7 N2 )4 (μ4 -tetraphos)] and [Au4 (CC–C10 H7 N2 )4 (μ4 -tpbz)] showed the involvement of all the gold atoms in close intramolecular Au⋯Au contact as well as intermolecular π stacking interactions between the aromatic rings of the polypyridyl ligands. The photophysical properties of the synthesized compounds were carefully studied and used as a probe of their possible use as multidentate ligands for Cu(i ) and Zn(ii ). The UV-Vis speciation studies of the complexation reactions were conducted via metal titration and, in most cases the dangling units of the ligand were found to behave in a fairy independent manner. While in the case of Cu(i ) multiple equilibria exist in solution a single complex is detected for Zn(ii ) under the conditions studied.