Reaction of [Mn(TTF-salphen)][OAc] (TTF-salphen2=2,2'-((2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3-benzodithiole- 5,6-diyl)bis(nitrilomethylidyne)bis(pbenolate)dianion) and the cyanometalate building blocks [n-Bu4N][(Tp)Fe(CN)3] (Tp =Tris(pyrazolyl)hydroborate) or [n-Bu4N][Ru(salen)(CN)2] (salen2 =N,N'-ethylenebis(salicylideneimine)dianion) resulted in the formation of two redox-active complexes, the dinuclear heterometallic complex [(Tp)Fe(CN)3Mn(TTF-salphen)'CH3OH] (1) and the one dimensional complex [Ru(salen)(CN)2Mn(TTF-salphen)]n (2). Both complexes were characterized by X-ray crystallography and solid state electrochemistry, in addition to static and dynamic magnetic measurements. Antiferromagnetic couplings are found to be operative between metal ion centers bridged by cyanide in both complexes. Complex 1 exhibited field-induced SMM behavior with an energy barrier of 13.8 K. The introduction of the redox-active TTF unit into cyanidebridged complexes with interesting magnetic properties renders them promising candidates for the construction of new hybrid inorganic-organic materials.
Long CuiFeifei ZhuChanel F.LeongJing RuFeng GaoDeanna M.D’AlessandroJinglin Zuo
Porous silicon (PSi) prepared from Pt metal-assisted chemical etching (MACE) was demonstrated to possess higher hydrosi- lylation efficiency (-57%) than anodized PSi (-11%) by surface reaction with co-undecenyl alcohol (UO). Deconvolution of the SiHx (x = 1-3) stretching bands revealed the abundance of SiH2 species on MaCE PSi was 53%, -10% higher than on ano- dized samples, while both of Sill1 and Sill3 were -5% lower correspondently on MaCE PSi than on anodized samples. The surface SiHx abundances were suggested to account for the higher hydrosilylation efficiency on MaCE PSi. Optimization of Pt-assisted chemical etching parameters suggested a 7-15 nm thick Pt-coating and an etching time of 3-10 min for biochip ap- plications. Scanning electron microscopy images revealed that an isotropic top meso-porous layer was beneficial for hydrosi- lylation and long-term durability under ambient conditions. To end, an example of histidine-tagged protein immobilization and microarray was illustrated. Combining the materials' property, surface chemistry, and micro-fabrication technology together, we envision that silicon based biochip applications have a prosperous future.