Reversible Structural Flexibility and Sensing Properties of a Zn(II) Metal–Organic Framework: Phase Transformation between Interpenetrating 3D Net and 2D Sheet

A three-dimensional Zn­(II) framework,
[Zn4O­(L)3(DMF)2]·0.5DMF·H2O (1; H2L = 3,3′-dimethoxybiphenyl-4,4′-dicarboxylic
acid) was prepared under a solvothermal reaction in DMF. The structure
reveals that the 3-fold interpenetration is stabilized in the framework
with a distinct secondary building unit of the formula [Zn4O­(R-CO2)6(DMF)2], slightly different
from that of MOF-5. Phase transformations in 1 occur
reversibly via two pathways of solvent exchange/resolvation and activation/resolvation,
which is indicative of the presence of extensive structural flexibility.
Nitrobenzene among tested solvents is selectively detected by 1, and the sensing event was operating repeatedly. The three-dimensional
framework of 1 with 3-fold interpenetration is uniquely
converted to the two-dimensional Cu phase with no interpenetration,
reflecting a drastic dimensionality variation.