Ultralong Persistent Room Temperature Phosphorescence of Metal Coordination Polymers Exhibiting Reversible pH-Responsive Emission

Abstract

Ultra-long-persistent room temperature phosphorescence (RTP) materials have attracted much attention and present various applications in illumination, displays, and the bioimaging field; however, the persistent RTP is generally from the inorganic phosphor materials to date. Herein, we show that the metal coordination polymers (CPs) could be new types of emerging long-lived RTP materials for potential sensor applications. First, two kinds of Cd-based CPs, Cd(m-BDC)(H2O) (1) and Cd(m-BDC)(BIM) (2) (m-BDC = 1,3-benzenedicarboxylic acid; BIM = benzimidazole), were obtained through a hydrothermal process, and the samples were found to exhibit two-dimensional layered structures, which are stabilized by interlayer C-H···π interaction and π···π interaction, respectively. The CPs show unexpected second-time-scale ultra-long-persistent RTP after the removal of UV excitation, and this persistent emission can be detected easily on a time scale of 0-10 s. The CPs also feature a tunable luminescence decay lifetime by adjusting their coordination situation and packing fashion of ligands. Theoretical calculation further indicates that the introduction of the second ligand could highly influence the electronic structure and intermolecular electron transfer toward tailoring the RTP of the CP materials. Moreover, CP 2 exhibits well-defined pH- and temperature-dependent phosphorescence responses. Therefore, this work provides a facile way to develop new type of CPs with steady-state and dynamic tuning of the RTP properties from both experimental and theoretical perspectives, which have potential applications in the areas of displays, pH/temperature sensors, and phosphorescence logic gates. On account of suitable incorporation of inorganic and organic building blocks, it can be expected that the ultra-long-persistent RTP CPs can be extended to other similar systems due to the highly tunable structures and facile synthesis routes.