Aqueous Solution Enhanced Room Temperature Phosphorescence through Coordination-Induced Structural Rigidity

Achieving aqueous solution enhanced room temperature phosphorescence (RTP) is critical for the applications of RTP materials in solution phase, but which faces a great challenge. Herein, for the first time, a strategy of coordination-induced structural rigidity is proposed to achieve enhanced quantum efficiency of aluminum/scandium-doped phosphorescent microcubes (Al/Sc-PMCs) in aqueous solution. The Al/Sc-PMCs in a dry state exhibit a nearly invisible blue RTP. However, they emit a strong RTP emission in aqueous solution with a RTP intensity increase of up to 22.16-times, which is opposite to common solution-quenched RTP. The RTP enhancement mechanism is attributed to the abundant metal sites (Al³⁺ and Sc³⁺ ions) on the Al/Sc-PMCs surface that can tightly combine with water molecules through the strong coordination. Subsequently, these coordinated water molecules as the bridging agent can bind with surface groups by hydrogen bonding interaction, thereby rigidifying chemical groups and inhibiting their motions, resulting in the transition from the nonradiative decay to the radiative decay, which greatly enhances the RTP efficiency of the Al/Sc-PMCs. This work not only develops a coordination rigidity strategy to enhance RTP intensity in aqueous solution, but also constructs a phosphorescent probe to achieve reliable and accurate determination of analyte in complex biological matrices.