Tetracene Diacid Aggregates for Directing Energy Flow Toward Triplet Pairs

Nicholas Pompetti, Kori Smyser, Benjamin Feingold, Raythe Owens, Bimala Lama, Sandeep Sharma, Niels Damrauer, Justin Johnson

Research output: Contribution to journalArticlepeer-review


A comprehensive investigation of the solution-phase photophysics of tetracene bis-carboxylic acid [5,12-tetracenepropiolic acid (Tc-DA)] and its related methyl ester [5,12-tetracenepropynoate (Tc-DE)], a non-hydrogen-bonding counterpart, reveals the role of the carboxylic acid moiety in driving molecular aggregation and concomitant excited-state behavior. Low-concentration solutions of Tc-DA exhibit similar properties to the popular 5,12-bis((triisopropylsilyl)ethynl)tetracene, but as the concentration increases, evidence for aggregates that form excimers and a new mixed-state species with charge-transfer (CT) and correlated triplet pair (TT) character is revealed by transient absorption and fluorescence experiments. Aggregates of Tc-DA evolve further with concentration toward an additional phase that is dominated by the mixed CT/TT state which is the only state present in Tc-DE aggregates and can be modulated with the solvent polarity. Computational modeling finds that cofacial arrangement of Tc-DA and Tc-DE subunits is the most stable aggregate structure and this agrees with results from 1H NMR spectroscopy. The calculated spectra of these cofacial dimers replicate the observed broadening in ground-state absorption as well as accurately predict the formation of a near-UV transition associated with a CT between molecular subunits that is unique to the specific aggregate structure. Taken together, the results suggest that the hydrogen bonding between Tc-DA molecules and the associated disruption of hydrogen bonding with solvent produce a regime of dimer-like behavior, absent in Tc-DE, that favors excimers rather than CT/TT mixed states. The control of aggregate size and structure using distinct functional groups, solute concentration, and solvent in tetracene promises new avenues for its use in light-harvesting schemes.
Original languageAmerican English
Pages (from-to)11473-11485
Number of pages13
JournalJournal of the American Chemical Society
Issue number16
StatePublished - 2024

NREL Publication Number

  • NREL/JA-5900-88872


  • absorption
  • mathematical methods
  • monomers
  • oligomers
  • solvents


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