One Fluorophore‐Two Sensing Films: Hydrogen‐Bond Directed Formation of a Quadruple Perylene Bisimide Stack

Abstract

Elaborately designed π-stacked molecular aggregates are significant for modulation of photophysical properties of polycyclic aromatic hydrocarbons (PAHs). Herein, a double hydrogen-bonds trussed di(pyridyl)pyrrole-perylene bisimide (HDPP-PBI) was designed and its dimerization behavior was studied. HDPP-PBI tends to form a quadruple PBI stack with a dimerization constant of ~5.56 × 10 6 M À 1 . The dimerization was ascribed to synergistic intramolecular double hydrogen-bonds formation and intermolecular π-π stacking. Addition of CF 3 COOH, a hydrogen bond blocker, promotes the dimer to monomer transition. Accordingly, two distinct fluorescent films were prepared by drop-casting of the dimerized or the monomeric HDPP-PBI onto a substrate surface. Interestingly, the less-emissive PBI quadruple stackbased film showed a turn on response to acetone vapor, while the highly emissive HDPP-PBI-based film exhibited fluorescence quenching upon exposure to triethylamine vapor. We believe that the discovered synergistic effect in the PBI aggregates would enlighten the design of new PAHs aggregates with defined structures.

Molecular design and architectonics towards film-based fluorescent sensing

“…4(g)). 98 Consequently, two distinct films were obtained from one fluorophore by modulating the quadruple aggregate and the monomeric state of PBI unit. The two sensing films demonstrate contrasting responses to triethylamine vapor and interferences, showcasing the potential for a single-fluorophore sensing array to offer enhanced selectivity and accuracy in sensing applications.…”

Advances in Molecular Design and Photophysical Engineering of Perylene Bisimide-Containing Polyads and Multichromophores for Film-Based Fluorescent Sensors

“…To fix the configuration of chromophores in a more powerful way, di(pyridyl)pyrrole-PBI (HDPP-PBI) with a double hydrogen-bonds was designed by us and successfully used as FFSs (Figure 5b). 45 In the presence of synergistic intramolecular double hydrogen-bond formation and intermolecular π−π stacking, HDPP-PBI was apt to form a quadruple PBI stack with a considerable dimerization constant. Such a dimer could effectively dissociate into monomer when trifluoroacetic acid, a hydrogen bond blocker, was added into the system.…”

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