Efforts are underway to develop protocols to obtain well-defined nanoclusters by templating their synthesis within a macromolecular ligand architecture featuring a specific number and type of binding sites. Three disparate families of polydentate ligands have been synthesized, utilizing a macrocyclic foundation as a preorganized framework: resorcin[4]arene; 1,4,7,10-tetrazacyclododecane (cyclen); and cis-1,2,3,4-tetramethanol cyclopentane. Ligand buttresses were installed to form tetra- or octa-dentate amine and alcohol ligands. Each ligand family was characterized by variable-temperature NMR studies and HRMS. Single-crystal x-ray crystallographic analysis confirmed their structures and the desired spatial orientation of the chelating ligand buttresses. Taken together, the polydentate ligands predispose nanocluster growth into one spatial dimension. Nanocluster formation proceeded through two general pathways: by an in situ deprotonation-metallation reaction with precursors like Fe2Mes4, [CuMes]5, Mn(HMDS)2, [Co(HMDS)2]2, and [Ni(HMDS)]4; or by ligand deprotonation (e.g. NaH or n-BuLi) followed by metallation using metal(I) or metal(II) halides (e.g. CuCl, FeCl2, CoCl2, NiCl2). The resulting products were analyzed by a range of spectroscopic (e.g. Mössbauer) and crystallographic techniques to determine the nanocluster structure. Solubility properties of the nanoclusters varied depending on tunable functional group substitutions of the ligand platforms and the stoichiometries of the metal sources. Nanoclusters soluble in organic solvents were imaged by TEM to confirm the monodispersity of the prepared material. In this talk I will describe our current efforts in the development of these families of clusters.

Cluster assembly with polydentate macrocycles: Synthesis of nanoscale particles with molecular definition

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.