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

Four isomorphic P2 chalcogenide clusters named [Sn11In9Cu6S44]·11(H+DBU) (1) (DBU = 1,8-diazabicyclo[5.4.0] undec-7-ene), [Sn10In10Cu6Se44]·6(H22+DMAPA)·2(DMAPA)·9EG (2) (DMAPA = 3-dimethylaminopropylamine, EG = ethylene glycol), [Sn10In10Cu6S40O4]·6[H22+PMDETA]·10EG (3) (PMDETA = pentamethyldiethylenetriamine), [Sn10Ga10Cu6S40O4]·6(H22+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.