Modification of metallic and non-metallic sites in pentasupertetrahedral chalcogenidometalate clusters for third-order nonlinear optical response.

Four isomorphic P2 chalcogenide clusters named [Sn 11 In 9 Cu 6 S 44 ]·11(H + DBU) (1) (DBU = 1,8-diazabicyclo[5.4.0] undec-7-ene), [Sn 10 In 10 Cu 6 Se 44 ]·6(H 2 2+ DMAPA)·2(DMAPA)·9EG (2) (DMAPA = 3-dimethylaminopropylamine, EG = ethylene glycol), [Sn 10 In 10 Cu 6 S 40 O 4 ]·6[H 2 2+ PMDETA]·10EG (3) (PMDETA = pentamethyldiethylenetriamine), [Sn 10 Ga 10 Cu 6 S 40 O 4 ]·6(H 2 2+ DMAPA)·7EG (4) have been isolated via organotin precursor and mixed-metal strategy. These clusters exhibit excellent solubility in organic solvents. The continuous-regulation of optical band and optical limiting performance have been realized through precise controlled substituting engineering of cationic and anionic elements.