Bridging and Conformational Control of Porphyrin Units through Non-Traditional Rigid Scaffolds
Date
2019-11-07
Authors
Grover, Nitika
Locke, Gemma M.
Flanagan, Keith J.
Beh, Michael H. R.
Thompson, Alison
Senge, Mathias O.
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Abstract
Connecting two porphyrin units in a rigid linear
fashion, without any undesired electron delocalization or
communication between the chromophores, remains a synthetic
challenge. Herein, a broad library of functionally diverse
multi-porphyrin arrays that incorporate the non-traditional
rigid linker groups cubane and bicyclo[1.1.1]pentane
(BCP) is described. A robust, reliable, and versatile synthetic
procedure was employed to access porphyrin-cubane/BCPporphyrin
arrays, representing the largest non-polymeric
structures available for cubane/BCP derivatives. These reactions
demonstrate considerable substrate scope, from utilization
of small phenyl moieties to large porphyrin rings, with
varying lengths and different angles. To control conformational
flexibility, amide bonds were introduced between the
bridgehead carbon of BCP/cubane and the porphyrin rings.
Through varying the orientation of the substituents around
the amide bond of cubane/BCP, different intermolecular interactions
were identified through single crystal X-ray analysis.
These studies revealed non-covalent interactions that are
the first-of-their-kind including a unique iodine-oxygen interaction
between cubane units. These supramolecular architectures
indicate the possibility to mimic a protein structure
due to the sp3 rigid scaffolds (BCP or cubane) that exhibit
the essential conformational space for protein function
while simultaneously providing amide bonds for molecular
recognition.
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Citation
Grover, N., Locke, G. M., Flanagan, K. J., Beh, M. H., Thompson, A., & Senge, M. O. (2020). Bridging and Conformational Control of Porphyrin Units through Non‐Traditional Rigid Scaffolds. Chemistry–A European Journal.