Activation and amplification of the third-order NLO and luminescent responses of a precursor cluster by a supramolecular approach.

Solvothermal reactions of [Et(4)N][TpWS(3)(CuCl)(3)] (1) (Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with CuCN and KCu(CN)(2) afforded two [Tp*WS(3)Cu(3)]-based coordination polymers Tp*WS(3)Cu(3)(μ(3)-DMF){Cu(CN)(3)} (2) and KTp*WS(3)Cu(3)(μ(3)-DMF){Cu(2)(CN)(4.5)} (3). The third-order NLO and PL responses of 1 were activated and greatly amplified through its assembly via the Cu(CN)(3) and Cu(4)(CN)(9) species in 2 and 3.