Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 80, Issue 3, Pages 1828-1840Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo502773g
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Funding
- National Science Foundation [CHE-1057411]
- University of Florida
- National Science Foundation REU program [CHE-1156907]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1057411] Funding Source: National Science Foundation
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The molecular recognition properties of the nucleobases instruct the formation of complex three-dimensional architectures in natural and synthetic systems; relatively unexplored is their use as building blocks for pi-conjugated materials where they might mutually tune electronic and supramolecular structures. Toward this goal, an introductory set (1a-d and 2a-d) of six purine-terminated and two pyrimidine-terminated p-conjugated oligomers has been synthesized and used to develop experimental electronic and photophysical structureproperty trends. Unlike 2,2':5',2?-terthiophene (TTT) derivatives 2a-d, intramolecular charge transfer dominates oligomers 1a-d bearing a 4,7-bisthienylbenzothiadiazole (TBT) spacer due to the strong electron-accepting ability of its benzothiadiazole (BTD) ring. The resulting donoracceptordonor systems feature lower HOMOLUMO gaps than the terthiophene-linked nucleobases (Delta E-g similar to 1.8 eV vs 2.4 eV based on electrochemical measurements), and the lowest so far for p-conjugated molecules that include nucleobases within the p-framework. Experiments reveal a dependence of photophysical and electronic structure on the nature of the nucleobase and are in good agreement with theoretical calculations performed at the B3LYP/6-31+G** level. Overall, the results show how nucleobase heterocycles can be installed within p-systems to tune optical and electronic properties. Future work will evaluate the consequences of these information-rich components on supramolecular p-conjugated structure.
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