Complementary Hydrogen Bonding Modulates Electronic Properties and Controls Self‐Assembly of Donor/Acceptor Semiconductors

Abstract

A comprehensive investigation of the complementary H-bonding-mediated self-assembly between dipyrrolo[2,3-b:3',2'-e]pyridine (P2P) electron donors and naphthalenediimide/perylenediimide (NDI/PDI) acceptors is reported. The synthesis of parent P2P and several aryl-substituted derivatives is described, along with their optical, redox, and single-crystal packing characteristics. The dual functionality of heteroatoms in the P2P/NDI(PDI) assembly, which act as proton donors/acceptors and also contribute to π-conjugation, leads to H-bonding-induced perturbation of electronic levels. Concentration-dependent NMR and UV/Vis spectroscopic studies revealed a cooperative effect of H-bonding and π-π stacking interactions. This H-bonding-mediated co-assembly of donor (D) and acceptor (A) components leads to a new charge-transfer (CT) absorption that can be controlled throughout the visible range. The electronic interactions between D and A were further investigated by time-dependent DFT, which provided insights into the nature of the CT transition. Electropolymerization of difuryl-P2P afforded the first conjugated polymer incorporating H-bonding recognition units in its main chain.

Strong Enhancement of π‐Electron Donor/Acceptor Ability by Complementary DD/AA Hydrogen Bonding

“…On the contrary, the orbital‐interaction effect (ii) causes a reverse negative‐charge transfer from the donor ( IC ) to the acceptor (quinone), which is more significant for stronger acceptors, hence explaining the trend of diminishing HLG decrease. Smaller changes (0.1 to 0.3 eV) in the orbital energies have been previously predicted for nucleobases and some D/A complexes . However, to the best of our knowledge, such a drastic perturbation of the HLG modulated by hydrogen bonding is unprecedented in π‐functional D/A systems.…”

“…Previously, we explored weak‐CT co‐assemblies of dipyrrolopyridine (P2P) donors and naphthalenediimide (NDI) acceptors mediated by complementary DAD/ADA H‐bonding and showed their functionality as dual( p / n )‐channel semiconductors in OFETs . Density‐functional‐theory (DFT) calculations suggested that H‐bonding leads to a small but consistent reduction of the HOMO–LUMO offset by 0.11–0.19 eV . We explained this perturbation by the partial dislocation of two protons from P2P to NDI, which results in a negative polarization on the P2P donor and a positive polarization on the NDI acceptor.…”

Synthesis of a Perylene Diimide Dimer with Pyrrolic N–H Bonds and N‐Functionalized Derivatives for Organic Field‐Effect Transistors and Organic Solar Cells

“…This was expected and confirms the loss of the tBOC group and transformation of 4 to 3. [22][23][24][25] These results show that the thermal deprotection strategy is effective at generating 3 in situ, and that 3 forms very stable thin films on glass (i.e.…”

Resonance Energy Transfer Emission Observed in Cocrystal of N,N′-Bis(3-imidazol-1-ylpropyl)naphthalenediimide with Cinnamic Acid

“…Such differences are due to extent of charge‐transfer between the acid and L, which is guided by the complementary hydrogen bonds. Such effect plays major role to tune optical properties . The observed colour differences have alerted us to explore stacking interactions of ‐ nap‐acid ‐ in these adducts.…”