Sequence controlled MOF-on-MOF microcrystals for multidomain liquid chromatography stationary phases

Designing liquid chromatography (LC) stationary phases with novel separation mechanisms is essential for advancing separation science. Herein, we report hierarchical metal-organic framework (MOF) stationary phases that integrate two distinct MOFs with different pore architectures, enabling multi-domain molecular recognition within a single crystalline material. Specifically [M₂(bdc)₂(ted)] _<i>n</i> (M-BDC; M = Cu or Zn, bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine) and [M₂(ndc)₂(ted)] _<i>n</i> (M-NDC; ndc = 1,4-naphthalenedicarboxylate) are employed as the inner (core) and outer (shell) phases to construct heteroepitaxial MOF-on-MOF architectures within individual crystals. By precisely controlling the growth sequence, MOF-on-MOF layered structures are formed, which are subsequently used as LC stationary phases. The retention behavior and separation performance of these MOF-on-MOF materials are evaluated using polycyclic aromatic hydrocarbons (PAHs) as probe analytes. The stationary phases exhibit distinct retention profiles depending on the heteroepitaxial sequence. In the M-NDC-on-M-BDC system, where the outer shell MOF has smaller pores than the core, the shell functions as an effective recognition layer, strongly influencing the retention behavior of the column even at low shell loading. Conversely, in the M-BDC-on-M-NDC system, where the shell MOF possesses larger pores, analytes can diffuse through the shell and interact with the core MOF, resulting in a reduced impact of the shell on the overall retention. These findings highlight that spatial arrangement and pore hierarchy within MOF-on-MOF architectures critically influence chromatographic behavior. This work demonstrates a new strategy for designing advanced MOF-based LC stationary phases based on modular MOF assembly.