Optoelectronically mismatched oligophenylethynyl-naphthalenediimide SHJ architectures.
The objective of this study was to evaluate the possibility of photoinduced stack/rod electron transfer in surface "zipper" architectures composed of stacks of blue (B) naphthalenediimides (NDIs) along strings of oligophenylethynyl (OPE) rods. The synthesis and characterization of anionic and cationic multichromophoric OPE-B systems are reported. Absorption spectra suggest that in OPE-B systems, planarity and thus absorption and conductivity of the OPE can possibly be modulated by intramolecular stacking of the surrounding NDIs, although interfering contributions from aggregation remain to be differentiated. Among surface architectures constructed with OPE-B and POP-B systems by zipper and layer-by-layer (LBL) assembly, photocurrents generated by OPE-B zippers exhibit the best critical thickness and fill factors. These findings confirm the existence and functional relevance of topologically matching zipper architectures. In OPE-B zippers, OPEs generate much more photocurrent than the blue NDIs. Ultrafast electron transfer from OPEs to NDIs accounts for these photocurrents, providing wavelength-controlled access to rod-stack charge separation, and thus to formal supramolecular n/p-heterojunctions (SHJs). NDI excitation is not followed by the complementary hole transfer to the OPE rod. Scaffolds with higher HOMOs will be needed to integrate blue NDIs into SHJ photosystems.
Maity
Santanu
S
Department of Organic, University of Geneva, Geneva, Switzerland.
Bhosale
Rajesh
R
Banerji
Natalie
N
Vauthey
Eric
E
Sakai
Naomi
N
Matile
Stefan
S
D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D004579:Electron Transport; D008968:Molecular Conformation; D015394:Molecular Structure; D053644:Naphthalimides / Q000138:chemical synthesis / Q000737:chemistry*; D010647:Phenyl Ethers / Q000138:chemical synthesis / Q000737:chemistry*; D010777:Photochemistry; D013053:Spectrophotometry
D000480:Alkynes; D053644:Naphthalimides; D010647:Phenyl Ethers