Decanuclear Gold(I) Sulfido Pseudopolymorphs Displaying Stimuli-Responsive RGBY Luminescence Changes

Abstract

Decanuclear gold(I) sulfido clusters, [Au 10 {μ-Ph 2 PN(R)PPh 2 } 4 (μ 3 -S) 4 ](PF 6 ) 2 ], with propeller-shaped structures were obtained using bridging bis(diphenylphosphino)amine with alkylpyridine pendant groups (R = −CH 2 Py, −CH 2 CH 2 Py). The cluster, [Au 10 {μ-Ph 2 PN(CH 2 −o-Py)PPh 2 } 4 (μ 3 -S) 4 ](PF 6 ) 2 , was found to crystallize in three different pseudopolymorphs with emission colors varying from blue to green to red. Unprecedented mechanochromic, solvatochromic, thermochromic, and acidochromic properties were also observed with RGBY emission colors. From the X-ray crystal structures and powder X-ray diffraction (PXRD) analysis, the luminescence changes were attributed to the transition between different pseudopolymorphs upon external stimulus.

Substituent-Mediated Transformation of Polynuclear Gold(I)-Sulfido Complexes—From Pentanuclear to Octadecanuclear Cluster-to-Cluster Transformation

“…The low-energy emission bands for these complexes near 570-710 nm can be assigned as arising from 3 LMMCT excited-state origin or 3 LMCT excited-state origin modified by metal⋯metal interactions, while the high-energy blue-green emission bands can be assigned as arising from the metal-perturbed ligand-centered phosphorescence, similar to that reported in previous studies. 65…”

Development of Dual Phosphorescent Materials Based on Multiple Stimuli-Responsive Ir(III) Acyclic Carbene Complexes

“…Therefore, the blue shift of the ground film upon acid fuming is not arisen from cis-to-trans isomerization but the N-protonation of the carbene complexes. 30,50,66 Due to the strong interactions between the N-H units of the protonated carbene ligand with the acetate anion, the cistrans isomerization of the carbene ligand is restricted. 30,50,66 As a result, the luminescent properties of the acid-fumed film (3-F ground-acid ) do not change upon mechanical grinding.…”

“…30,50,66 Due to the strong interactions between the N-H units of the protonated carbene ligand with the acetate anion, the cistrans isomerization of the carbene ligand is restricted. 30,50,66 As a result, the luminescent properties of the acid-fumed film (3-F ground-acid ) do not change upon mechanical grinding. With this chemical reactivity, the mechanochromic behavior can be gated, as illustrated in Scheme 2.…”

Heteroctanuclear Au4Ag4 Cluster Complexes of 4,5-Diethynylacridin-9-One with Luminescent Mechanochromism

“…As a class of mechanically sensitive compounds, a number of d 10 metal complexes [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 ] have been found to show remarkable luminescent mechanochromism due to mostly the formation or disruption of d 10 -d 10 intermetallic interactions under the stimulus of mechanical actions such as crushing, grinding, stretching. Over the years, we have been devoted to the design of d 8 -d 10 and d 10 -d 10 heterometallic cluster complexes as phosphorescent materials for the use in solution-processed organic light-emitting diodes (OLEDs), taking advantage of aromatic acetylides as bridging ligands [ 24 ].…”