Supramolecular Gold(I) Thiobarbiturate Chemistry:  Combining Aurophilicity and Hydrogen Bonding to Make Polymers, Sheets, and Networks

Abstract

The cooperative forces of aurophilic and hydrogen bonding have been used in the self-assembly of phosphine or diphosphine complexes of gold(I) with the thiolate ligands derived from 2-thiobarbituric acid, SC(4)H(4)N(2)O(2), by single or double deprotonation. The reaction of the corresponding gold(I) trifluoroacetate complex with SC(4)H(4)N(2)O(2) gave the complexes [Au(SC(4)H(3)N(2)O(2))(PPh(3))], 1, [(AuSC(4)H(3)N(2)O(2))(2)(micro-LL)], with LL = Ph(2)PCH(2)PPh(2), 2a, Ph(2)P(CH(2))(3)PPh(2), 2b, or Ph(2)PCH=CHPPh(2), 2c, or the cyclic complex [Au(2)(micro-SC(4)H(2)N(2)O(2))(micro-Ph(2)PCH(2)CH(2)PPh(2))], 3. In the case with LL = Ph(2)P(CH(2))(6)PPh(2), the reaction led to loss of the diphosphine ligand to give [Au(6)(SC(4)H(3)N(2)O(2))(6)], 4, a hexagold(I) cluster complex in which each gold(I) center has trigonal AuS(2)N coordination. Structure determinations show that 1 has no aurophilic bonding, 2b, 3, and 4 have intramolecular aurophilic bonding, and 2c has intermolecular aurophilic bonding that contributes to the supramolecular structure. All the complexes undergo supramolecular association through strong NH...O and/or OH...N hydrogen bonding, and complex 3 also takes part in CH...O hydrogen bonding. The supramolecular association leads to formation of interesting polymer, sheet, or network structures, and 4 has a highly porous and stable lattice structure.

The supramolecular chemistry of gold and l -cysteine: Formation of photoluminescent, orange-emitting assemblies with multilayer structure

“…Regarding the latter, it has been concluded that the layers consist of hexagonally arranged gold and sulfur atoms with arrays of the peptide ligands bulging perpendicularly to the plane [29]. In other works on Au-thiolates such as Au-thiomalate or Au-phenylthiolate, zigzag shaped chains of the polymers with and alternating arrangement of ligand molecules have been proposed [13,32,33]. Luminescent gold(I) acetylides with the same shape have been reported [34].…”

Dipodal Ferrocene‐Based Adsorbate Molecules for Self‐Assembled Monolayers on Gold

“…The intramolecular AuÀAu distance is 3.336(1) , which is essentially identical to the distance be- The structural and functional similarities of aurophilic and hydrogen bonding have been emphasized in recent studies. [28] In particular, a striking structural similarity between isocyanide complexes MeA C H T U N G T R E N N U N G (CH 2 ) nÀ1 NCAuCl and primary…”

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

“…[30][31][32][33][34][35][36] In addition to coordinative bonding, a multitude of interactions have been used in the synthesis of periodic networks including covalent bonding, [37] hydrogen bonding, [38][39][40] p-p interactions, [41][42][43] ionic interactions, [44,45] lipophilic interactions, [46,47] metalmetal interactions, [48][49][50] and halogen bonding. [51,52] However, the deliberate use of cation-p interactions to control the assembly of extended networks has received little attention.…”