Solution-Processable Metal-Organic Framework Featuring Highly Tunable Dynamic Aggregation States.

Abstract

The limited processability of metal-organic frameworks (MOFs) is hindered flexibility in the manipulation of their aggregation state and applications. Therefore, achieving highly processable MOFs is of great significance but a challenging goal. Herein, a facile strategy is presented for achieving the construction of solution-processable Mg-based MOF, NKU-Mg-1, allowing for dynamic control of the aggregation state through dynamic self-assembly (DySA) process and reversible circularly polarized luminescence (CPL) switcher modulation. Notably, micron-sized crystals of NKU-Mg-1 can be readily dispersed in water to form nano-sized colloids, triggered by the dynamic COO-Mg coordination bonding interruption by the competitive H₂O-Mg bonding. Accordingly, the aggregation state of the colloid MOF can be readily tuned from 50-80 nm up to 1000 nm, in turn enabling control of aggregation-dependent emission. Specially, the solid-phase aggregation can be controlled via structural transitions between 3D NKU-Mg-1-rec-1 and 2D NKU-Mg-1-rec-2 nano-crystals, as confirmed by 3D electron diffraction. Furthermore, benefiting from its highly dynamic tunable aggregation nature, the rational incorporation of the chiral module confers significant CPL activity (g_lum up to 0.01). Importantly, controllable dynamic aggregation enables reversible switching of the CPL activity by precisely regulating the aggregation states. The solution-processable and dynamic aggregation-tunable features endow it highly promising for applications.