Interfacial self-assembly of Cd2+-tetraphenylethylene coordination polymers and their photophysical properties in Langmuir-Blodgett films

Molecular arrangement and orientation of tetraphenylethylene (TPE) unit in the highly ordered thin films and aggregates can effectively limit its conformation that results in strong effect on the excited energy transfer process and luminescent behaviors under irradiation. We report here an interfacial self-assembly of metal-TPE coordination polymer (CP) ultrathin films and their aggregate-induced emission (AIE) behaviors. After connected with pyridyl or benzimidazole substituents, the tetradentate TPEs as synthesized are used as the multidentate linkers to coordinate with the Cd2+ ions to produce aggregates in the solutions, and to form well-defined two- and three-dimensional organized Cd-TPE CP multilayers at the air-water interfaces by the LangmuirBlodgett (LB) method. It is revealed that, in addition to the aggregation-induced emission, the following external factors have also large effects on the luminescence of TPEs, including the coordination bonding in the CPs, in plane and interlayer molecular interaction in the LB films; both of them can restrict the intramolecular motion or rotation of TPE unit. Because of these external effects, the emission lifetime of TPEs reaches to approximately 5-10 times longer in some Cd-TPE CP LB films than that in the solutions. Further, the luminescent emission wavelengths and colors of LB films can be tuned to some extent by the in-plane and interlayer molecular interaction. Finally, it is demonstrated that the luminescent emissions , colors of the Cd-TPPE CP LB films is selectively sensing to methanol and formic acid in the gas phase with good reversibility and reproductivity.

Automated summary

The molecular arrangement and orientation of tetraphenylethylene (TPE) unit in thin films and aggregates have a strong impact on the energy transfer process and luminescent behaviors. In this study, metal-TPE coordination polymer (CP) ultrathin films are self-assembled at the air-water interfaces, showing aggregate-induced emission (AIE) behaviors. The luminescence of TPEs in CPs and LB films is influenced by the coordination bonding and molecular interactions, which lead to longer emission lifetime and tunable emission wavelengths and colors. Moreover, the Cd-TPE CP LB films exhibit selective sensing to methanol and formic acid in the gas phase.