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Solid-state [2+2] photocycloaddition in an interpenetrated Mn(II)-based metal-organic framework via a single-crystal-to-single-crystal transformation
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DOI：10.1002/bkcs.70122.png)
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Abstract
En 中文
Metal-organic frameworks (MOFs) are structurally tunable crystalline materials that can undergo stimulus-induced transformations in the solid state. Herein, we report a light-induced manganese(II)-based MOF, [Mn(bpe)(tdc)]& centerdot;2DMA (1), incorporating olefinic 1,2-bis(4-pyridyl)ethylene (bpe) ligands. MOF 1 crystallizes in the monoclinic C2/c space group and features Mn(II) centers with distorted octahedral coordination geometries. The yellow block-shaped crystals adopt a double-pillared pcu topology with parallel alignment of bpe ligands, in which the olefinic C=C bonds are separated by 4.016 angstrom, satisfying Schmidt's criteria for solid-state [2 + 2] photocycloaddition. Upon ultraviolet irradiation, MOF 1 undergoes a [2 + 2] photocycloaddition reaction to form [Mn-2(rctt-tpcb)(tdc)(2)]& centerdot;2DMA (2). Single-crystal X-ray diffraction analysis confirms the formation of cyclobutane rings in MOF 2 while preserving the pcu topology, parallel two-fold interpenetration, and overall crystallinity. Despite the covalent bond formation and structural rearrangement, the coordination environments of the Mn(II) centers remain intact. This work demonstrates a rare example of a single-crystal-to-single-crystal photochemical transformation in a Mn(II)-based MOF and highlights the potential of rational structural design for controlling solid-state photoreactivity.
Keywords:
[2+2] photocycloaddition reaction
manganese(II)
metal-organic frameworks
single-crystal-to-single-crystal transformation
solid-state photoreactivity
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