Supramolecular Assembly of Trimeric Gold(I) Pyrazolates through Aurophilic Attractions

Abstract

The supramolecular architecture of trinuclear gold(I) pyrazolato aggregates is held together by intermolecular aurophilic attractions, sterically governed by the substituents on the pyrazole rings. A two-dimensional network of [Au(mu-pz)]3 complexes, 1 (pz = pyrazolato anion, C3H3N2-), and a large intricate aggregate of 16 [Au(mu-4-Me-pz)]3 complexes in 2 have been determined crystallographically. Under UV irradiation at ambient temperature, solid samples of 1 and 2 luminesce with lambda max = 626 and 631 cm-1, respectively, attributed to intermolecular Au...Au aurophilic contacts.

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

“…These kinds of ligands have a proven ability to hold metal atoms in close proximity while permitting a wide range of intermetallic separations, being useful in the synthesis of shape-persistent macrocycles, such as the homonuclear [M I A C H T U N G T R E N N U N G (m-Rpz)] 3 (M = Cu, [36][37][38][39][40][41][42] Ag, [37,38,43,44] Au; [43,[45][46][47][48][49][50] Rpz = pyrazolate or substituted pyrazolate) or [M II 3 A C H T U N G T R E N N U N G (m-Rpz) 6 ] (M II = Pd [51,52] Pt [52,53] ) as the heteronuclear clusters [Pd 2 M 2 A C H T U N G T R E N N U N G (m-Rpz) 6 ] (M = Cu, Ag, Au), [52,54] and [M 2 M' 4 A C H T U N G T R E N N U N G (m-Rpz) 8 ] (M = Pd, Pt; M' = Cu, Ag). [52,55] Apart from the interest arising from their structural diversity, some of these pyrazolate bridging complexes have also been shown to be excellent systems for examining metallophilic interactions [49,[56][57][58][59][60][61][62] and as luminescent materials. [49,[56][57][58][59][63]…”

“…[52,55] Apart from the interest arising from their structural diversity, some of these pyrazolate bridging complexes have also been shown to be excellent systems for examining metallophilic interactions [49,[56][57][58][59][60][61][62] and as luminescent materials. [49,[56][57][58][59][63][64][65][66] One of the synthetic strategies used to obtain the above-mentioned heteropolynuclear pyrazolate complexes is the replacement of the proton in coordinated pyrazoles by the metal ions: Cu I , Ag I , and Au I . The self-assembly of the resulting units gives the heterometallic clusters.…”

Synthesis and crystal structures of copper(II) and silver(I) complexes of a semi-rigid bipyrazolyl ligand

“…1H-Pyrazole usually acts as a monodentate ligand; its deprotonated form, namely pyrazolido ion, can behave in exo-bidentate or multidentate bridging fashions with typical MÁÁÁM distances of ca 3.3 Å [1][2][3][4]. Bipyrazolyl ligands, in which two pyrazolyl units are linked via covalent bonds, are expected to exhibit more versatile coordination patterns, and therefore be more useful in construction of complicated supramolecular architectures.…”

Synthesis and characterization of 2-aminobenzoimidazolate group 11 coordination polymers: A combined X-ray powder diffraction and 13CP MAS NMR study

“…These compounds have shown to possess valuable functional properties, such as high thermal stability [1], magnetic hysteresis [2], and luminescence [3], as well as anticorrosive [4], sorption [5] and protein staining [6] activities.Transition metal imidazolates (or analogous ligands) typically possess simple formulation, rigid nature and highly predictable coordination geometry. In spite of this, they have afforded a variety of structural types, ranging from 1D chains, to 2D layers and 3D networks [7], showing, occasionally, crystalline polymorphic species with distinct topologies and spectroscopic features [8].…”

“…These compounds have shown to possess valuable functional properties, such as high thermal stability [1], magnetic hysteresis [2], and luminescence [3], as well as anticorrosive [4], sorption [5] and protein staining [6] activities.…”