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Measurements of the third-order nonlinear optical responses of solutions of the metal-metal multiply bonded complexes Mo(2)(OPr(i))(6), W(2)(OBu(t))(6), M(2)(NMe(2))(6), M(2)(O(2)CBu(t))(4), and M(2)Cl(4)(PMe(3))(4) (M = Mo, W), using picosecond degenerate four-wave mixing at 1064 nm, are reported. These complexes display only very small instantaneous electronic polarizations when excited with cross-polarized beams. When the excitation beams are similarly polarized, a significant third-order optical response is detected, which is attributable to the formation of bulk thermal excitation gratings. Time-dependent measurements support this view.

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In the title complex, [Sm(C(9)H(9)F(5)NSi)(3)(C(4)H(8)O)], the Sm metal center is coordinated in a highly distorted tetrahedral geometry by the three N atoms of the amido ligands and by the O atom of the tetrahydrofuran ligand. Principal bond lengths include: Sm-N 2.299 (4), 2.339 (4) and 2.366 (4) A, and Sm-O 2.446 (3) A, close Sm. F contacts of 2.536 (3) and 2.556 (3) A, and an 'agostic' Sm.C interaction of 3.154 (4) A.