Photochemical reactivity of two gold(I) dinuclear complexes, cis/trans-(AupNBT)2dppee: Isomerization for the cis-(AupNBT)2dppee isomer, radical substitution for trans-(AupNBT)2dppee

Photoinduced single-crystal-to-single-crystal phase transition and photosalient effect of a gold(i) isocyanide complex with shortening of intermolecular aurophilic bonds

“… 15 However, solid-state phase changes of gold complexes where the photoinduced change of aurophilic interactions is a dominant factor have not been reported. 16 …”

“…To the best of our knowledge, this report is also the first observation of solid-state photochromism in a gold complex. 16 The colorless 1B phase, a crystallized form of the gold( i ) isocyanide complex 1 , exhibits blue photoluminescence ( Fig. 1 ).…”

Photoinduced Isomerization-Driven Structural Transformation Between Decanuclear and Octadecanuclear Gold(I) Sulfido Clusters

“…On the other hand, cis–trans isomerization can frequently be observed in CC, , CN, , and NN , bond containing derivatives, which have been widely used to design and synthesize functional molecular switches . Generally, the trans forms of these double bond based compounds are thermodynamically more stable than the cis forms. , Bruce and co-workers have reported that the trans isomer of the uncoordinated 1,2-bis­(diphenylphosphino)­ethene (dppee) ligand is 23 kJ mol –1 more stable than cis -dppee . Nevertheless, the free cis -dppee could not undergo isomerization upon photoirradiation. , By coordination to gold­(I), several dinuclear gold­(I) cis -dppee complexes have been demonstrated to possess photochemical isomerization reactivity .…”

“…Generally, the trans forms of these double bond based compounds are thermodynamically more stable than the cis forms. , Bruce and co-workers have reported that the trans isomer of the uncoordinated 1,2-bis­(diphenylphosphino)­ethene (dppee) ligand is 23 kJ mol –1 more stable than cis -dppee . Nevertheless, the free cis -dppee could not undergo isomerization upon photoirradiation. , By coordination to gold­(I), several dinuclear gold­(I) cis -dppee complexes have been demonstrated to possess photochemical isomerization reactivity . However, to the best of our knowledge, similar photoisomerization properties have never been applied to the polynuclear gold­(I) cluster system.…”

“…Here we report the unprecedented photoinduced isomerization-driven structural reconfiguration of polynuclear gold­(I) complexes. The chlorogold­(I) precursors, cis -[dppee­(AuCl) 2 ] and trans -[dppee­(AuCl) 2 ] (Chart ), , have been employed to assemble luminescent polynuclear gold­(I) μ 3 -sulfido clusters, 1 (Au 10 ) and 2 (Au 18 ), respectively. Interestingly, the decagold­(I) cluster could be quantitatively transformed to octadecagold­(I) clusters in solution, mediated by the transformation of the organic ligands from cis - to trans -dppee, which could be monitored by 31 P­{ 1 H} NMR, UV–vis absorption, and emission spectroscopy.…”