Non-linear optical materials containing molybdenum or tungsten mononitrosyl redox centres: diaromatic azo derivatives

Authors:
  • BCBenjamin J. Coe
    Benjamin J. Coe
  • JFJean-Dominic Foulon
    Jean-Dominic Foulon
  • THThomas A. Hamor
    Thomas A. Hamor
  • CJChristopher J. Jones
    Christopher J. Jones
  • JMJon A. McCleverty
    Jon A. McCleverty
  • DBDavid Bloor
    David Bloor
  • GCGraham H. Cross
    Graham H. Cross
  • TATony L. Axon
    Tony L. Axon
Publisher website
Google Scholar
Abstract
The following compounds have been prepared: [M(NO)L(X)n{EC6H3(R-3)[NNC6H3(R′-3)(R″-4)-4]}2 – n][L = tris(3,5-dimethylpyrazolyl)hydroborate; R″=(η5-C5H4)Fe(η5-C5H5), E = O, R = R′= H, M = Mo, X = Cl or I, n= 0 or 1; E = NH, R = R′= H, n= 1, M = Mo or W, X = Cl; E = NH, R = Me, R′= H, n= 1, M = Mo, X = F, Cl, Br, I or OC6H11; M = W, X = Cl; E = NH, R = R′= Me, n= 1, M = Mo, X = Cl or I; M = W, X = Cl; R″= NMe2, E = O, R = R′= H, M = Mo, X = Cl or I. n= 0 or 1; M = W, X = Cl, n= 1; E = NH, R = R′= H, n= 1, M = Mo, X = Cl or I; M = W, X = Cl], [M(NO)-L(X){OC10H6[NNC6H4(OEt-4)-4]}](M = Mo, X = Cl or I; M = W, X = Cl) and [Mo(NO)L(Cl)-(NHC6H3(Me-3){NNC6H3(Me-3)[NNC6H3(Me-3)(R″-4)-4]}-4)]. Several of the ferrocenyl derivatives have been found to produce frequency doubling of radiation at 1907 nm, whereas the derivatives containing NMe2 or OEt groups do not. A single-crystal X-ray diffraction study has shown that [W(NO)LCl{NHC6H3(Me-3)[NNC6H4(R″-4)]-4}]·CH2Cl2 crystallises in the space group P21 and is isostructural with its molybdenum counterpart; in these crystals the molecules appear to be favourably oriented to produce phase matching.