Synthesis, crystal structure and second-order nonlinear optical properties of the trinuclear palladium orthometalated complex [(mu(3)-S)(mu(3)-OH) Pd-3((CN)-N-boolean AND)(3)] ((HCN)-N-boolean AND = p-((Bu2N)-N-n)-C6H4-CH=N-C6H4-NO2-p)

摘要

A smooth reaction of [(mu(2)-OH)(2)Pd-2((CN)-N-boolean AND)(2)] (3) with CS2 center dot((HCN)-N-boolean AND = p-((Bu2N)-N-n)-C6H4-CH=N-C6H4-NO2-p) provides [(mu(3)-S)(mu(3)-OH)Pd-3((CN)-N-boolean AND)(3)] (4). The X-ray structures of 4 shows that the complex contains a (mu(3)-S)(mu(3)-OH)Pd-3 core which forces an all-cis arrangement of the three orthometalated ligands. The variation of the beta(0) value per imine moiety, on going from the free imine to the trinuclear complex (4) is negative: -17%. In contrast, for the dinuclear complexes [(mu(2)-SBu)(mu(2)-OAc)Pd-2((CN)-N-boolean AND)(2)] (5) or [(mu(2)-SBu)(mu(2)-Cl)Pd-2((CN)-N-boolean AND)(2)] (6), having also a cis-arrangement of the orthometallated imines, this variation is positive: +14% and +30%, respectively. The beta(0) variation seems to be concordant with the trend of the molar extinction coefficients values.