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Diana M Stefanescu

Publications and source records attributed to Diana M Stefanescu.

4 recordsLinked to original sources

Bifunctional, conjugated oligomers for orthogonal self-assembly: selectivity varies from planar substrates to nanoparticles.

A diphenylacetylene containing two different end groups (isonitrile and thioacetate) was synthesized, showing that the chemistry used to install each end group is compatible with that of the others. The isonitrile group binds preferentially to platinum, and the thiol group binds preferentially to gold. However, the selectivity was different when nanoparticles were compared to planar substrates.

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Synthesis and characterization of phosphido-monolayer-protected gold nanoclusters.

Gold-phosphido-monolayer-protected clusters (MPCs) of 1-2-nm diameter, Au(x)(PR2)y, analogues of the well-known thiolate materials Au(x)(SR)y, were prepared by NaBH4 reduction of a mixture of HAuCl4.3H2O and a secondary phosphine PHR2 in tetrahydrofuran/water. In comparison to the Au-thiolate MPCs, fewer of the larger phosphido groups are required to cover the surface, and the Au-P bond is not cleaved as readily in reactions with small molecules as is its Au-S counterpart. 31P NMR spectroscopy provides a direct method to study cluster formation and the interaction of the phosphido ligand with the gold surface.

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Gold(I) phosphido complexes: synthesis, structure, and reactivity.

Deprotonation of the phosphine complexes Au(PHR(2))Cl with aqueous ammonia gave the gold(I) phosphido complexes [Au(PR(2))](n)() (PR(2) = PMes(2) (1), PCy(2) (2), P(t-Bu)(2) (3), PIs(2) (4), PPhMes (5), PHMes (6); Mes = 2,4,6-Me(3)C(6)H(2), Is = 2,4,6-(i-Pr)(3)C(6)H(2), Mes = 2,4,6-(t-Bu)(3)C(6)H(2), Cy = cyclo-C(6)H(11)). (31)P NMR spectroscopy showed that these complexes exist in solution as mixtures, presumably oligomeric rings of different sizes. X-ray crystallographic structure determinations on single oligomers of 1-4 revealed rings of varying size (n = 4, 6, 6, and 3, respectively) and conformation. Reactions of 1-3 and 5 with PPN[AuCl(2)] gave PPN[(AuCl)(2)(micro-PR(2))] (9-12, PPN = (PPh(3))(2)N(+)). Treatment of 3 with the reagents HI, I(2), ArSH, LiP(t-Bu)(2), and [PH(2)(t-Bu)(2)]BF(4) gave respectively Au(PH(t-Bu)(2))(I) (14), Au(PI(t-Bu)(2))(I) (15), Au(PH(t-Bu)(2))(SAr) (16, Ar = p-t-BuC(6)H(4)), Li[Au(P(t-Bu)(2))(2)] (17), and [Au(PH(t-Bu)(2))(2)]BF(4) (19).

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