Highly Sterically-Crowded Subvalent Group 14 Compounds: Unexpected Structures and High Reactivity with Small Molecules

A series of new compounds, MAr2 (M = Ge, Sn, or Pb; Ar = terphenyl ligands) display structures and structural trends that are counter-intuitive with regard to steric effects. These trends are also reflected in their spectroscopic properties and in their reaction chemistry. It was found that the presence or absence of substituents at apparently-remote sites on the ligands can exert a large influence on the course of the reactions, as well as on the structural characteristics of the group 14 element environment.

Supramolecular Approaches to Advanced Functional Materials


In the "bottom-up" approach, materials and devices are constructed from molecules capable of assembling themselves by principles/methods of molecular recognition. Although well-defined assemblies can be engineered by exploiting various noncovalent interactions, there are limited methods in the literature regarding the design and analysis of self-guiding molecules for materials application in which there is a strategic integration of the self-assembling motif.  The principal research conducted in the Watkins Group encompasses fundamental studies towards understanding the molecular assembly of complex systems as it relates to overall performance. Reported are design guidelines towards novel building blocks for functional materials—specifically those for applications in optoelectronic devices and biomaterials. The multi-step synthesis of these building blocks is discussed.  Spectroscopic analysis, as well as characterization via transmission electron microscopy (TEM) and X-ray crystallography of the molecular components and their resulting supramolecular assemblies, reveal materials possessing properties that are comparable to—even surpass—those commonly reported in the literature.  Results of this study will be employed towards further research in novel molecular components capable of yielding high performing materials.


Professor Ken Hsu is featured in the Future of Biochemistry, the special issue of the ACS publication Biochemistry.  This special issue features the work of 44 Junior Faculty that were selected from across the globe who are combining an ever-diversifying set of skills and backgrounds to tackle problems of biochemical relevance. See the Introductory Editorial and Dedication that lists Professor Ken Hsu here.

Phosphorus-Element Bond-Forming Reactions

White phosphorus (P4) has been the traditional entry point into phosphorus chemistry. The thirteenth element to have been isolated, it can be oxidized with elemental oxygen or chlorine, or reduced in a variety of ways. We investigated its reduction using early transition metal systems and breakdown to produce complexes with terminal metal-phosphorus triple bonds. Such terminal phosphide complexes possess nucleophilic phosphorus atoms, paving the way to new phosphorus-element bonded systems.


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