Research: Structural Chemistry

X-ray Crystallography

Many of the novel compounds synthesized in the Senge group are characterized by single crystal X-ray diffractometry to determine atomic structure. Knowing the shape and bonding patterns of molecules is critical to rationalizing and predicting properties, and to designing molecules for specific applications. Additionally, a crystal structure is an important verification tool for new medicinal compounds and gives information on intermolecular interactions to a precision not realized by any other technique. In exploratory organic chemistry, crystal structure analysis is important in confirming regioselectivity of reactions and offers a complementary technique to NMR.

A periodic table of NSD distortions
Normal-coordinate Structural Decomposition

The continued development of computational methods related to normal-coordinate structural decomposition (NSD), initally developed by John Shelnutt, allows for grouping of porphyrin macrocycles by class, based on their structural characteristics. Designing systems which adopt highly distorted shapes is essential to promoting the activation of the porphyrin core H-atoms for sensing or catalysis. Research in the group has shown that porphyrins are biased towards only a few distortion modes, and these are predictably accessed via simple substitution patterns. The NSD routine is able to be run on your own samples in .pdb format, at NSD Link

Over 1000 porphyrin crystal structures have been determined by group members past and present. We are currently using structural insights from single crystal studies, alongside cutting edge data science techniques in diverse fields, to inform the design of 'smart' materials . We are pioneering advances in crystal engineering for environmental and medical applications.

The in-plane and out-of-plane distortions of the porphyrin core 2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5,15-diphenylporphyrinato-NiII