Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5394264 | Computational and Theoretical Chemistry | 2012 | 6 Pages |
Using quantum chemical (QC) calculations at the B3LYP/6-31G(d) level of theory, we investigate for three selected layer-pillar paddle-wheel metal-organic framework materials of composition M2IIL21L2(MII=Zn,Cu;L1=2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate, 2,3,5,6-tetramethylbenzene-1,4-dicarboxylate; L2 = 1,4-diazabicylco[2.2.2]octane) the preferential orientations and the rotational energy barriers of both layer (L1) and pillar (L2) linkers. The calculations suggest unhindered rotational motion for pillar linker in all compounds studied (ÎEbarrier ⩽ 0.14 kcal molâ1). For layer linkers, the energy barriers for the rotation of benzene rings are found to vary significantly, indicating an hindered rotation in the case of the fluorine substituent (ÎEbarrier â 14 kcal molâ1), and a static situation in the case of the methyl substituent (ÎEbarrier â 75 kcal molâ1). The rotational dynamics are found not to depend on the type of metal ion. AIM analysis indicates that the rotational energy barriers are influenced by C-Hâ¯F hydrogen-bonding interactions between the dabco and fluorine-substituted linkers.
Graphical abstractDownload full-size imageHighlights⺠Linker rotational motion in paddle-wheel MOFs were studied using QC calculations. ⺠The calculations suggest an unhindered rotational motion for the pillar linker. ⺠The ÎEbarrier indicates a hindered rotation in the case of fluorine substituent. ⺠The C-Hâ¯F hydrogen-bonding causes ÎEbarrier between the dabco and F-substituent. ⺠The different of ÎEbarrier lead to the rotational dynamics in mixed-linker MOFs.