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<p>Metal-organic frameworks (MOFs) incorporating multiple functional groups provide modular platforms for tailoring physical properties and photochemical reactivity. We report the synthesis and comparative photoreactivity analysis of a set of iso-reticular Zn(II)-based MOFs constructed from 1,4-bis[2-(3-pyridyl)ethenyl]benzene and benzene-1,4-dicarboxylate linkers bearing diverse substituents. These frameworks, comprising single-component, multivariate (MTV), and core-shell architectures, undergo [2+2] photocycloaddition in the solid state via a single-crystal-to-single-crystal transformation under UV irradiation. Real-time photoreaction dynamics were monitored by laser scanning confocal microscopy, revealing functional group-dependent variations in emission behavior and reaction kinetics. MTV-MOFs exhibit two distinct photoreactivity patterns: either consistent with, or markedly divergent from, the predicted linear combination of the respective single-component analogues, suggesting non-trivial linker-linker interactions. In contrast, core-shell MOFs retain the intrinsic photoreactivity and luminescence profiles of each domain, indicative of minimal interfacial coupling. These findings underscore the critical influence of linker identity, spatial arrangement, and compositional distribution on MOF photoreactivity, providing valuable insights for the rational design of photoresponsive crystalline materials.</p>

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Spatial modulation of photoreactivity in isoreticular metal-organic frameworks: comparative insights into single-component, multivariate, and core-shell systems

  • 期刊论文

  • 发表日期：

    2026年7月27日

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  • Ziyue Liu,
  • Qi Liu,
  • Jianping Lang

摘要

Metal-organic frameworks (MOFs) incorporating multiple functional groups provide modular platforms for tailoring physical properties and photochemical reactivity. We report the synthesis and comparative photoreactivity analysis of a set of iso-reticular Zn(II)-based MOFs constructed from 1,4-bis[2-(3-pyridyl)ethenyl]benzene and benzene-1,4-dicarboxylate linkers bearing diverse substituents. These frameworks, comprising single-component, multivariate (MTV), and core-shell architectures, undergo [2+2] photocycloaddition in the solid state via a single-crystal-to-single-crystal transformation under UV irradiation. Real-time photoreaction dynamics were monitored by laser scanning confocal microscopy, revealing functional group-dependent variations in emission behavior and reaction kinetics. MTV-MOFs exhibit two distinct photoreactivity patterns: either consistent with, or markedly divergent from, the predicted linear combination of the respective single-component analogues, suggesting non-trivial linker-linker interactions. In contrast, core-shell MOFs retain the intrinsic photoreactivity and luminescence profiles of each domain, indicative of minimal interfacial coupling. These findings underscore the critical influence of linker identity, spatial arrangement, and compositional distribution on MOF photoreactivity, providing valuable insights for the rational design of photoresponsive crystalline materials.