Base-assisted synthesis of 4-pyridinate gold(i) metallaligands: a study of their use in self-assembly reactions. Issue 23 (24th May 2021)

• Record Type: Journal Article
• Authors: Ferrer, Montserrat; Gutiérrez, Albert; Martínez, Manuel; Da Silva, Cristiana; Netto, Adelino V. G.; Rodríguez, Laura; Romo-Islas, Guillermo; Pan, Fangfang; Rissanen, Kari
• Is Part Of: Dalton transactions. Volume 50:Issue 23(2021)
• Page Start: 8154
• Page End: 8166
• Publication Date: 2021-05-24
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt00402f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Self-assembly reactions between di- and tritopic gold(i ) metallaligands bearing terminal pyridine rings and Pd(ii ) or Pt(ii ) fragments produce heterometallic macrocycles and cages with cavities of different sizes and shapes. Abstract : The synthesis of di- and tritopic gold(i ) metallaligands of the type [(Au4-py)2 (μ2 -diphosphane)] (diphosphane = bis(diphenylphosphanyl)isopropane or dppip (1 ), 1, 2-bis(diphenylphosphanyl)ethane or dppe (2 ), 1, 3-bis(diphenylphosphanyl)propane or dppp (3 ) and 1, 4-bis(diphenylphosphanyl)butane or dppb (4 )) and [(Au4-py)3 (μ3 -triphosphane)] (triphosphane = 1, 1, 1-tris(diphenylphosphanylmethyl)ethane or triphos (5 ) and 1, 3, 5-tris(diphenylphosphanyl)benzene or triphosph (6 )) from [(AuCl)2 (μ2 -diphosphane)] or [(AuCl)3 (μ3 -triphosphane)] and 4-pyridylboronic acid in the presence of Cs2 CO3 has been conducted. Interestingly, when [(AuCl)2 (μ2 -dppm)] (dppm = bis(diphenylphosphanyl)methane) was used as a starting material, the cyclic tetranuclear gold(i ) compound [(Au4-py)2 (CH)2 {μ2 -Au(PPh2 )2 }2 ] (I ) was obtained instead. All the products have been characterized by IR and multinuclear NMR spectroscopy, mass spectrometry and elemental analysis and in the case of 1, 3, 5 and I by X-ray crystallography, which showed the presence of aurophilic interactions in all of them. The obtained metallaligands have been used as building blocks in self-assembly reactions with cis -blocked palladium or platinum acceptor moieties producing [2 + 2] metallamacrocycles or trigonal bipyramidal (TBP) [2 + 3] metallacages in good yields. The photophysical properties of both the metallaligands and the corresponding assemblies have been investigated.