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Polymers 2018, 10(9), 1014; https://doi.org/10.3390/polym10091014

Sponge-Like Water De-/Ad-Sorption versus Solid-State Structural Transformation and Colour-Changing Behavior of an Entangled 3D Composite Supramolecuar Architecture, [Ni4(dpe)4(btc)2(Hbtc)(H2O)9]·3H2O

1
Department of Chemistry, Soochow University, Taipei 11102, Taiwan
2
National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
3
Instrumentation Center, National Taiwan University, Taipei 10617, Taiwan
4
Department of Chemistry, Fu Jen Catholic University, Xinbei 24205, Taiwan
*
Authors to whom correspondence should be addressed.
Received: 26 August 2018 / Revised: 8 September 2018 / Accepted: 8 September 2018 / Published: 11 September 2018
(This article belongs to the Special Issue Advances in Coordination Polymers)
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Abstract

An entangled composite compound, [Ni4(dpe)4(btc)2(Hbtc)(H2O)9]·3H2O (1), where H3btc = 1,3,5-benzenetricarboxylic acid and dpe = 1,2-bis(4-pyridyl)ethane, has been synthesized and structurally characterized. Single-crystal structural determination reveals that compound 1 consists of four coordination polymers (CPs), with two two-dimensional (2D) (4,4) layered metal-organic frameworks (MOFs) of [Ni(dpe)(Hbtc)(H2O)] and [Ni(dpe)(btc)(H2O)] anion, and two one-dimensional (1D) polymeric chains of [Ni(dpe)(btc)(H2O)3] anion and [Ni(dpe)(H2O)4]2+ cation, respectively. The three-dimensional (3D) supramolecular architecture of 1 is constructed via the inter-penetration of inter-digited, double-layered, 2D rectangle-grid MOFs by two 1D coordination polymeric chains, and tightly entangled together via the combination of inter-CPs π–π stacking and hydrogen bonding interactions. The ad-/de-sorption isotherms of 1 for water displays a hysteresis profile with a maximum adsorption of 17.66 water molecules of per molecule unit at relative P/P0 < 0.89. The reversible de-/re-hydration processes in 1 monitored by cyclic water de-/ad-sorption TG analysis and PXRD measurements evidence a sponge-like water de-/ad-sorption property associated with a thermal-induced solid-state structural transformation. The magnetic property of 1 suggests that the ferromagnetic coupling might refer to a stronger inter-Ni(II) interaction, which could be along the btc3− or Hbtc2− ligands; the antiferromagnetic coupling corresponding to the weaker inter-Ni(II) interactions, which could be the dpe ligands for the 2D framework. View Full-Text
Keywords: coordination polymer; metal-organic framework; supramolecular architecture; structural transformation; photoluminescence; magnetic property coordination polymer; metal-organic framework; supramolecular architecture; structural transformation; photoluminescence; magnetic property
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Wang, C.-C.; Ke, S.-Y.; Chen, K.-T.; Sun, N.-K.; Liu, W.-F.; Ho, M.-L.; Lu, B.-J.; Hsieh, Y.-T.; Chuang, Y.-C.; Lee, G.-H.; Huang, S.-Y.; Yang, E.-C. Sponge-Like Water De-/Ad-Sorption versus Solid-State Structural Transformation and Colour-Changing Behavior of an Entangled 3D Composite Supramolecuar Architecture, [Ni4(dpe)4(btc)2(Hbtc)(H2O)9]·3H2O. Polymers 2018, 10, 1014.

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