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Perylene-Diimide Helicenes: A New Molecular Architecture for Chiral Electronics

Schuster, Nathaniel Joseph

Perylene-3,4,9,10-tetracarboxylic diimide (PDI) has emerged as a building block of organic materials for next generation molecular electronics. Intensely absorbing and chemically robust, PDI-based materials often excel as n-type semiconductors in organic field-effect transistors and organic photovoltaic (OPV) cells. Notably, twistacene nanoribbons arising from the iterative fusion of PDI to ethylene have been incorporated into OPV cells with power conversion efficiencies approaching 10%. These PDI-twistacenes adopt various unresolvable isoenergetic conformations in solution, precluding the possibility of optical activity.
In pursuit of persistent helical chirality in PDI-based nanoribbons, I have prepared and now present naphthyl- and anthracenyl-linked PDI-dimer helicene (NPDH and APDH). Their syntheses entail the cross-coupling of an acene to two PDI subunits, followed by oxidative ultraviolet cyclizations. Straining the polyaromatic surface does not encumber the efficiency of these photocyclizations: they proceed quantitatively, without a trace of the sterically favored regioisomers. We have resolved NPDH and APDH into their constituent enantiomers by chiral high performance liquid chromatography. Solutions of APDH racemize at room temperature, whereas NPDH does not invert at 250 °C. The enantiostability of NPDH arises from the extensive intramolecular overlap of its π-surface. Looking down its stereogenic axis reveals ten pairs of π-bonded atoms eclipse one another. The nearest of these pairs are separated by 3.2 Å, closer than twice the van der Waals radius of the carbon atom. Thus, the naphthyl link of NPDH facilitates intramolecular π-to-π collisions between the PDI subunits. Voltammetric, spectroelectrochemical, and EPR measurements suggest these π-to-π collisions enable through-space electronic delocalization when NPDH is reduced.
I next report the preparation of a π-helix of helicenes constituted from three PDI monomers and two naphthalene subunits. Two different synthetic routes of alternating cross-couplings and oxidative photocyclizations provided this nanoribbon, naphthyl-fused PDI-trimer helix (NP3H). Remarkably, visible light from household lightbulbs induces these cyclizations, although the final cyclization proceeds more swiftly when on the helix exterior than when within its core. NP3H possesses extraordinary chiroptical properties, exhibiting numerous and incredibly intense electronic circular dichroism (ECD) across the UV-visible range (|Δε| = 820 M-1 cm-1 at 407 nm). The ECD spectrum of NP3H transforms significantly in the presence of a mild reducing agent and visible light. Spectroelectrochemical measurements confirmed that photoinduced electron transfer to the π-helix tunes its absorbance of circularly polarized light.


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More About This Work

Academic Units
Thesis Advisors
Nuckolls, Colin P.
Ph.D., Columbia University
Published Here
October 20, 2017