A Reversible Polymorphic Phase Change Which Affects the Luminescence and Aurophilic Interactions in the Gold(I) Cluster Complex, [μ₃-S(AuCNC₇H₁₃)₃](SbF₆)

Abstract

Crystallographic examination of [mu3-S(AuCNC7H13)3](SbF6) shows that it undergoes a reversible phase change from orthorhombic to monoclinic upon cooling. At 190 K, the structure shows that two cations self-associate to form a pseudo-octahedral array of six gold atoms connected by both intra- and interionic aurophilic interactions. On cooling, the clusters become less symmetric, and in one, the interionic Au...Au separations increase, while they decrease in the second cluster. The luminescence of crystalline [mu3-S(AuCNC7H13)3](SbF6) shows corresponding changes in emission, with two emissions of similar lifetimes but with different excitations at 77 K, but only a single emission at 298 K. In contrast, [mu3-S(AuCNC6H11)3](PF6), which has a similar structure to that of the high-temperature form of [mu3-S(AuCNC7H13)3](SbF6), does not undergo a phase change or change in its luminescence upon cooling.

Remarkable Luminescence Behaviors and Structural Variations of Two-Coordinate Gold(I) Complexes

“…In the solid state, [µ 3 -S(Au I CNC 7 H 13 ) 3 ](SbF 6 ) forms a dimeric unit that contains a pseudo-octahedral arrangement of gold ions that interact through both intra-and inter-ionic interactions as seen in Fig. 12 [42]. Remarkably, cooling the crystal results in a reversible polymorphic phase change that produces lengthening of the aurophilic interactions in one pair of cations while inducing shortening of those in a second pair of cations, as seen in Scheme 2 below.…”

“…Thus, these emissions are both likely to result from phos- show the excitation spectra for emission at 680 and 490 nm, respectively. From [42] phorescence. The emission at 680 nm has an excitation spectrum with a maximum at 340 nm, while the emission at 490 nm has an excitation maximum at 387 nm.…”

Structural characterization of dinuclear gold(I) diphosphine complexes with anion-triggered luminescence

“…and/or chemical (solvents, guests, anions, etc.) stimuli [14][15][16][17][18][19][20]. The solid-state luminescence, however, strongly depends on molecular structure and molecular packing modes modulated by the interplay of non-covalent interactions such as aurophilic, hydrogen bonding or π···π interactions that are sensitive to external stimuli [14].…”

AuI⋅⋅⋅AuI Interaction Assisted Host–Guest Interactions and Stimuli‐Responsive Self‐Assembly in Tetranuclear Alkynylgold(I) Calix[4]arene‐Based Isocyanide Complexes

“…[8,14] Gold(I) alkynyls and isocyanidesh ave been utilized as common ligand systems of gold(I) complexes. Various examplesm aking use of the gold(I)isocyanides and alkynylsf or the design and synthesis of clusters, [17] polymorphic materials [17,18] andm echanochromic materials [19] have been reported.B ased on the early work on dinuclear gold(I) thiolates with switching on of Au I ···Au I interaction upon potassium ion-binding, [20] Yama nd co-workers have also employedaseries of alkynylcalix [4]arene-based gold(I) complexes as highlys elective chemosensors forv arious metal ions. Various examplesm aking use of the gold(I)isocyanides and alkynylsf or the design and synthesis of clusters, [17] polymorphic materials [17,18] andm echanochromic materials [19] have been reported.B ased on the early work on dinuclear gold(I) thiolates with switching on of Au I ···Au I interaction upon potassium ion-binding, [20] Yama nd co-workers have also employedaseries of alkynylcalix [4]arene-based gold(I) complexes as highlys elective chemosensors forv arious metal ions.…”