New self-defocusing materials: synthesis, structures and nonlinear optical properties of nest shaped clusters

Abstract

Mixed metal clusters (n-Bu4N)2[MoCu3OS3X3] (X = SCN, Cl and Br) were synthesized by solid state reactions. X-ray single crystal diffraction data show that the anionic clusters assume nest shaped structures. The clusters exhibit large self-defocusing effect as demonstrated by their Z-scan traces. The effective third-order polarizability of |γ| = 4.8 × 10-29 esu was determined for (n-Bu4N)2[MoCu3OS3(SCN)3] by a degenerate four-wave mixing technique with 7-ns laser pulses of 532 nm wavelength. An irradiance-dependent transmission measurement was conducted to assess the contribution of nonlinear absorption to the γ-value. These results in combination with the self-defocusing property of the cluster yielded a negative value for the real part of γ, Reγ = - 4.8 × 10-29 esu. These numerical values are in good agreement with those obtained in a Z-scan experiment. Even though the clusters absorb laser light at 532 nm significantly, the results of temporal profile analysis on transmitted pulses show that the solvent thermal effect makes little contribution to the observed nonlinear optical phenomenon.