Unconventional Pyridyl Ligand Inclusion within a Flexible Metal‐Organic Framework Bearing an N,N′‐Diethylformamide (DEF)‐Solvated Cd5 Cluster Secondary Building Unit

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Abstract
A cationic three‐dimensional (3D) metal‐organic framework (MOF) sustained by an N,N′‐diethylformamide (DEF)‐solvated zigzag‐shaped Cd5 cluster secondary building unit (SBU), [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ 4.75DEF (1 a, H3BTB=benzene‐1,3,5‐tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl3 to yield [Et2NH2]2[Cd5(BTB)4(DEF)2] ⋅ xCHCl3 (1 b) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd2+ could not be replaced by strongly donor pyridyl and dipyridyl ligands. Additionally, more electron‐deficient pyridyls preferentially coordinated to the flanking Cd2+ of the Cd5 SBU, as exemplified by [Et2NH2]2[Cd5(BTB)4(DEF)2(PyCHO)2] ⋅ xSol (2 a, PyCHO=4‐pyridinealdehyde) and [Et2NH2]2[Cd5(BTB)4(DEF)2(PyAc)2] ⋅ xSol (2 b, PyAc=4‐acetylpyridine). Density functional theory (DFT) calculations were used to understand these counterintuitive observations.
Funding Information
  • National Natural Science Foundation of China (21871203, 21671143)

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