Gold catenanes

Abstract

a b s t r a c tA review is given of the chemistry of gold catenanes following the discovery by Mingos of the first molecular gold [2]catenane in the alkynylgold(I) complex [{Au(CC-t-Bu)} 6 ] 2 . Because gold centers are typically labile towards ligand substitution, there may be an easy equilibrium between linear and cyclic gold oligomers and aurophilic attractions can promote the formation of catenanes from cyclic gold(I) oligomers. As well as molecular catenanes, there is also an extensive chemistry of catenanes anchored to gold surfaces or to gold nanoparticles.

Coordination-Directed Construction of Molecular Links

“…In addition, interlocked molecules with robust covalent skeletons have also been obtained directly through the entwining and threading of organic strands via hydrogen bonding, stacking interactions, anion coordination, or a combination of these noncovalent interactions. − Furthermore, natural interlocked species have been found in biological systems, , such as knotted polynucleotide chains and protein architectures. A number of excellent reviews provide further reading and insights into specific aspects of known examples of interlocked architectures. − …”

Solvent‐Induced Cluster‐to‐Cluster Transformation of Homoleptic Gold(I) Thiolates between Catenane and Ring‐in‐Ring Structures

“…guest [3d,4a-f,h,5] interactions have been reported, together with some examples of ring-in-ring metal complexes,inwhich the two noninterlocked rings were constructed or held together by metal-ligand coordination bonds [7b,d,8-10] (such as M-N (M = Cu, [8a] Pd, [9a,c, 10a,b] Ru, [7b,d, 8b] Ir, [9d] Pt, [9c] Zn [4g] )a nd M-O bonds (M = Ru, [9b] Ir [9d] ), for example,F igure 1d-f) or held together by p-p stacking (Figure 1d,f) [7c,9] or hydrophobic interactions. [10] Closed-shell metallophilic interactions are comparable in strength with atypical hydrogen bond, [11] and have been used in the formation of catenanes,a sd emonstrated by the [2]catenane structures in, for example,t he homoleptic homometallic Au I -alkynyl or -thiolate complexes [Au(CC-tBu)] 12 , [12] [Au(CCR)] 10 , [13] [Au(SR)] n (n = 10, [14] 11, [15] 12 [14] ), heteroleptic Au I -alkynyl/phosphine complexes, [16] and heterometallic Cu I /Ag I /Au I -alkynyl complexes, [17b] and also the [3]catenane structure for Cu I -alkynyl complexes [17a, 18] such as [Cu(CCtBu)] 20 .T he previous works on Au I -alkynyl or -thiolate catenanes highlight the role of Au I ···Au I interactions in the assembly of interlocked rings.H owever,t othe best of our knowledge,t he assembly of ar ing-in-ring complex in which the noninterlocked rings are held together by closedshell metallophilic interactions has not been reported.…”

Self-assembly of the smallest and tightest molecular trefoil knot

“…This article describes the synthesis of a trefoil Au 6 metallaknot ( Au 6 ) with only 54 atoms in the backbone (BCR = 18). It was prepared simply by self-assembly of units of a digold(I) diacetylide and a diphosphine ligand, a method previously reported to yield only gold catenane structures 22 . Characterization by single crystal X-ray diffraction provides convincing evidence that Au 6 represents both the smallest and the tightest molecular knot known to date.…”