Binuclear cluster-to-cluster-based supramolecular compounds: Design, assembly, and enhanced third-order Nonlinear optical performances of {[Et4N](2)[MoOS3Cu2(mu-CN)](2)center dot 2aniline}(n) and {[Et4N](4)[MoOS3Cu3CN(mu'-CN)](2)(mu-CN)(2)}(n)

Reaction of a cluster precursor [Et4N](2)[MoOS3(CuCN)] (1) with equimolar [Cu(MeCN)(4)](PF6) in MeCN/aniline gave rise to an interesting polymeric cluster {[Et4N](2)[MoOS3Cu2(mu-CN)](2)center dot 2aniline), (2), while treatment of I in MeCN with 2 equiv of CuCN and KCN in H2O afforded the other polymeric cluster {[Et4N](4)[MoOS3Cu3CN(mu'-CN)](2)(mu-CN)(2)}(n) (3). Generated by addition of one or two Cu+ onto the [MoOS3Cu] Cluster core in 1, the butterfly shaped [MoOS3Cu2] fragment in 2 or the incomplete cubanelike [MoOS3Cu2] fragment in 3 was dimerized into a prismatic [MoOS3Cu2] cage core or a double incomplete cubanelike [MoOS3Cu2] core. These two expanded cores serve as a unique planar 4-connecting node (2) or a rare chairlike 4-connecting node (3) to link equivalent nodes via cyanide bridges, forming two kinds of different 2D (4,4) networks. The third-order nonlinear optical (NLO) properties of 1-3 in DMF were also investigated.