Organic structures have now established themselves as key materials for a variety of advanced applications, including power generation (photovoltaics, thermoelectrics), solid-state lighting, sensors, and nanoelectronics. Our research is focused on cross-conjugated carbon-rich materials. Cross-conjugated materials are known to allow the control of intramolecular charge-transport [1], which would offer great promise for single-molecule electronics. By incorporating cross-conjugated motifs into shape-persistent macrocycles, we hope to exploit self-assembly into columnar structures. To this end, a series of tetrabenzo[18]cyclynes(TBCs) has been synthesized. [2]Here, we report the synthesis and characterization of hexyloxy-substituted triphenylene-based TBCs. One of the key structural features of these macrocycles is their pronounced oblong shape. NMR and fluorescence measurements suggest aggregation into dimers in chloroform. DFT calculations of the changes in proton chemical shifts for candidate dimers have been used to estimate the geometry of the dimer. Photophysical properties of the new macrocycle will also be discussed.Reference:[1] Thompson, A. L.; Ahn, T.-S.; Thomas, K. R. J.; Thayumanavan, S.; Mart�nez, T. J.; Bardeen, C. J. J. Am. Chem. Soc. 2005 , 127, 16348�16349.[2] Leu, C.W.; Fritz, A.E.; Digianantonio, K.M.; Grundy, S.C.; Hartley, C.S. J. Org. Chem. 2012 , 77, 2285�2298.

Oblong shape-persistent macrocycles: Synthesis and solution-phase dimerization

248th National Meeting (2014)

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