Structural and nonlinear optical properties of aligned heterotrinuclear [Ru(II)-(Spacer)-M(II)-(Spacer)-Ru(II)] complexes (M = Pd, Pt; spacer = 4-ethynylpyridine).
Lewis addition between the metalloligand [RuCp(C[triple bond]Cpy-4)(dppf)] (1) (dppf = (C(5)H(4)PPh(2))(2)Fe) and MCl(2)(CH(3)CN)(2) gives [RuCp(C[triple bond]Cpy-4)(dppf)](2)[MCl(2)] (M = Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d(6)-d(8)-d(6) metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuCl(C[triple bond]Cpy-4)(dppm)(2)] (4) and [trans-RuCl(C[triple bond]Cpy-4)(dppm)(2)](2)[MCl(2)] (dppm = Ph(2)PCH(2)PPh(2)) (M = Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized Ru(III) better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The gamma(real) value of the PdRu(2) dppm complex 5 is among the largest for linear organometallic complexes.
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore), Fax: (+65) 6873-1324.
Qingchun
Q
Ge
Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia), Tel: (+02) 6125-2927.
Gulliver T
GT
Dalton
Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia), Tel: (+02) 6125-2927.
Mark G
MG
Humphrey
Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, 50379 Wroclaw (Poland).
Marek
M
Samoc
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore), Fax: (+65) 6873-1324.
T S Andy
TSA
Hor