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. 2018 Jul 24:6:306.
doi: 10.3389/fchem.2018.00306. eCollection 2018.

Controlling Thermal Expansion Behaviors of Fence-Like Metal-Organic Frameworks by Varying/Mixing Metal Ions

Hao-Long Zhou  1 , Jie-Peng Zhang  1 , Xiao-Ming Chen  1   2
Affiliations

Controlling Thermal Expansion Behaviors of Fence-Like Metal-Organic Frameworks by Varying/Mixing Metal Ions

Hao-Long Zhou et al. Front Chem. .

Abstract

Solvothermal reactions of 3-(4-pyridyl)-benzoic acid (Hpba) with a series of transition metal ions yielded isostructral metal-organic frameworks [M(pba)2]·2DMA (MCF-52; M = Ni2+, Co2+, Zn2+, Cd2+, or mixed Zn2+/Cd2+; DMA = N,N-dimethylacetamide) possessing two-dimensional fence-like coordination networks based on mononuclear 4-connected metal nodes and 2-connected organic ligands. Variable-temperature single-crystal X-ray diffraction studies of these materials revealed huge positive and negative thermal expansions with |α| > 150 × 10-6 K-1, in which the larger metal ions give the larger thermal expansion coefficients, because the increased space not only enhance the ligand vibrational motion and hinged-fence effect, but also allow larger changes of steric hindrance between the layers. In addition, the solid-solution crystal with mixed metal ions further validates the abundant thermal expansion mechanisms of these metal-organic layers.

Keywords: flexibility; metal ion radius; metal-organic framework; porous coordination polymers; pyridyl-carboxylate; solid solution; structure-property relationship; thermal expansion.

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Figures

Figure 1
Figure 1
Perspective views of the crystal structure of [M(pba)2]·2DMA. (A) Coordination environment of the metal node. (B) The metal-organic fence, and the definition of its interior angle. (C) The stacking structure of metal-organic fences with DMA as guests, which are highlighted in pink. Metal ion: orange, C: dark gray, H: light gray, N: blue, O: red.
Figure 2
Figure 2
The stacking mode of the metal-organic fences. (A) Top view of the stacking layers. (B) Side view of the stacking layers. (C) Stacking of the tetrahedral building units of adjacent layers (highlighted in the space-filling mode). (D) The key atoms of adjacent tetrahedral building units.
Figure 3
Figure 3
Thermal expansion behaviors of [M(pba)2]·2DMA.
Figure 4
Figure 4
Elucidation of the thermal expansion mechanism for the fence stacking. (A) The tetrahedral building unit. (B) The selected parameters and variations for the geometry of the tetrahedral building unit and the interlayer separation/interaction. (C) Schematic views of thermal expansion upon the change of steric hindrance and metal ions.
Figure 5
Figure 5
SEM and EDS images of [Zn0.77Cd0.23(pba)2]·2DMA. (A) SEM image of [Zn0.77Cd0.23(pba)2]·2DMA. (B) EDS image of zinc. (C) EDS image of cadmium.
See this image and copyright information in PMC

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References

    1. Cai W. Z., Katrusiak A. (2014). Giant negative linear compression positively coupled to massive thermal expansion in a metal-organic framework. Nat. Commun. 5:4337. 10.1038/ncomms5337 - DOI - PubMed
    1. Chang Z., Yang D. H., Xu J., Hu T. L., Bu X. H. (2015). Flexible metal-organic frameworks: recent advances and potential applications. Adv. Mater. 27, 5432–5441. 10.1002/adma.201501523 - DOI - PubMed
    1. Chapman K. W., Chupas P. J., Kepert C. J. (2005). Direct observation of a transverse vibrational mechanism for negative thermal expansion in Zn(CN)2: an atomic pair distribution function analysis. J. Am. Chem. Soc. 127, 15630–15636. 10.1021/ja055197f - DOI - PubMed
    1. Chapman K. W., Chupas P. J., Kepert C. J. (2006). Compositional dependence of negative thermal expansion in the Prussian blue analogues MPtIVPtII(CN)6 (M = Mn, Fe, Co, Ni, Cu, Zn, Cd). J. Am. Chem. Soc. 128, 7009–7014. 10.1021/ja060916r - DOI - PubMed
    1. Chen S., Shang R., Wang B. W., Wang Z. M., Gao S. (2015). An a-site mixed-ammonium solid solution perovskite series of [(NH2NH3)x(CH3NH3)1-x][Mn(HCOO)3] (x = 1.00-0.67). Angew. Chem. Int. Ed. 54, 11093–11096. 10.1002/anie.201504396 - DOI - PubMed

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