The synthesis of the 1st generation dendrimer 1,3,5-{trans-[Ru(C≡C-3,5-(trans-[Ru(C≡CPh)(dppe)(2) (C≡CC(6) H(4) -4-(E)-CHCH)])(2) C(6) H(3) )(dppe)(2) (C≡CC(6) H(4) -4-(E)-CHCH)]}(3) C(6) H(3) proceeds by a novel route that features Emmons-Horner-Wadsworth coupling of 1,3,5-C(6) H(3) (CH(2) PO(OEt)(2) )(3) with trans-[Ru(C≡CC(6) H(4) -4-CHO)Cl(dppe)(2) ] and 1-I-C(6) H(3) -3,5-(CH(2) PO(OEt)(2) )(2) with trans-[Ru(C≡CPh)(C≡CC(6) H(4) -4-CHO)(dppe)(2) ] as key steps. The stilbenylethynylruthenium dendrimer is much more soluble than its ethynylated analog 1,3,5-{trans-[Ru(C≡C-3,5-(trans-[Ru(C≡CPh)(dppe)(2) (C≡CC(6) H(4) -4-C≡C)])(2) C(6) H(3) )(dppe)(2) (C≡CC(6) H(4) -4-C≡C)]}(3) C(6) H(3) and, in contrast to the ethynylated analog, is a two-photon absorber at telecommunications wavelengths.

Supporting informationfor this articleisa vailable on the WWW under http://dx.doi.org/10.1002/cplu.201500220. It contains complete details of the syntheses and characterization of compounds 1-5, 7,a nd 8,and complexes 9a-e, 10, 11 a-c, 13 a, 14 a-c, 15 a-c, 16 a, 16 b, 17 a, 17 b, and 18;crystallographic studies of 9c-e, 11 a, 12',and 12'';electrochemical studies of all new complexes;s pectroelectrochemical studies of 14 a-14 c;s ingle-wavelength nonlinear optical studies of 15 a-c, 16 b, 17 a, 17 b,and 18;and broad-spectral-range nonlinearo pticals tudies of 9d, 9e, 14 a-c,and 18.Part of aS pecialI ssue to celebrate Singapore'sG olden Jubilee. To view the complete issue,visit:http://dx.Scheme1.Syntheseso fa cetylenes 5 and 8.Scheme6.Syntheses of ene-linkage-containing "wedge" complexes 17 a and 17 b.[Ru] = trans-[Ru{k 2 -PPh 2 (CH 2 ) n Ph 2 } 2 ][ n = 1( dppm),2(dppe)].