[WS₃Cu₂] cluster.based supramolecular frame: Assembly, structure, and third.order nonlinear optical response

Reactions of (Et4N)(Tp*WS3) (A) ( Tp*=hydridotris(3,5- dimethylpyrazol- 1- yl)borate) and Cu.. salts [Cu(MeCN)4]PF6 with di(pyridin-4-yl)sulfane ( L-1) or bis(4-( pyridin-4-yl)phenyl)methanone ( L2) gave rise to two W/Cu/ S cluster-based supramolecular compounds with the formula of [Tp*WS3Cu2(L-1)]2(PF6) 2 center dot 2MeCN center dot 2CHCl(3) (1 center dot 2MeCN center dot 2CHCl(3)) and [Tp*WS3Cu2( L-2)(MeCN)](2)(PF6) 2 center dot 4MeCN (2 center dot 4MeCN), respectively. Both cluster- based supramolecular compounds were structurally characterized by single- crystal X- ray diffraction, 1H NMR, MS, IR, UV- Vis, and elemental analysis. Single crystal X- ray diffraction demonstrates that both compounds are cationic cluster- based supramolecule frames with similar butterfly- like cores. H-1 NMR and high- resolution electrospray ionization mass spectrometry (HRESI- MS) demonstrated their stability in DMF solution. In addition, the Z - scan measurement reveals the third-order nonlinear optical responses of 1 center dot 2MeCN center dot 2CHCl(3) and 2 center dot 4MeCN were enhanced compared to that of their precursor A. CCDC: 2257638, 1 center dot 2MeCN center dot 2CHCl3; 2257639, 2 center dot 4MeCN.