Metal Organo-Polymeric Framework via [2 + 2] Cycloaddition Reaction

Influence of Hydrogen Bonding on Depolymerization

In Hyeok Park, Kenta Sasaki, Hong Sheng Quah, Eunji Lee, Masaaki Ohba, Shim Sung Lee, Jagadese J. Vittal

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

In the doubly interpenetrated metal-organic framework (MOF) structure with cds topology, [Zn 2 (bpeb)(dhbdc)(fa) 2 ], 1 (where bpeb = trans,trans,trans-1,4-bis[2-(4′-pyridyl)ethenyl]benzene, dhbdc = 2,5-dihydroxy-benzene-1,4-dicarboxylate, and fa = formate), the adjacent bpeb ligands are aligned in a slip-stacked manner infinitely, and the olefin pairs are aligned in parallel ready to undergo a quantitative photochemical [2 + 2] cycloaddition reaction. The single-crystal-to-single-crystal (SCSC) photoreaction under UV light yielded a non-interpenetrated [Zn 2 (poly-bppcb)(dhbdc)(fa) 2 ], 2 (where poly-bppcb = 1,3-(4,4′-bipyridyl)-2-phenylcyclobutane) in which the poly-bppcb polymer comprising cyclobutane rings are nicely integrated into the two-dimensional coordination polymeric sheet formed by [Zn 2 (dhbdc)(fa) 2 ]. This organic polymer can be depolymerized back to 1 by heating 2 at 250 °C in a hot air oven for 6 h. The cleavage of cyclobutane rings to bpeb ligands has been attributed to the hydrogen bonding of the two hydroxy groups in the dhbdc ligand. In a similar metal organo-polymeric framework with bdc ligand, the poly-bppcb could not be depolymerized. Thus, this study provided some new insights into the reversible cleavage of cyclobutane polymers. These polymeric materials based on cyclobutane may be environmentally benign as these can be depolymerized to yield easily disposable and degradable monomers.

Original languageEnglish
Pages (from-to)1996-2000
Number of pages5
JournalCrystal Growth and Design
Volume19
Issue number3
DOIs
Publication statusPublished - Mar 6 2019

Fingerprint

Cyclobutanes
depolymerization
cyclobutane
Depolymerization
Cycloaddition
cycloaddition
Hydrogen bonds
Metals
Ligands
ligands
formic acid
hydrogen
metals
cleavage
Benzene
Polymers
polymers
benzene
Single crystals
high temperature air

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Metal Organo-Polymeric Framework via [2 + 2] Cycloaddition Reaction : Influence of Hydrogen Bonding on Depolymerization. / Park, In Hyeok; Sasaki, Kenta; Quah, Hong Sheng; Lee, Eunji; Ohba, Masaaki; Lee, Shim Sung; Vittal, Jagadese J.

In: Crystal Growth and Design, Vol. 19, No. 3, 06.03.2019, p. 1996-2000.

Research output: Contribution to journalArticle

Park, In Hyeok ; Sasaki, Kenta ; Quah, Hong Sheng ; Lee, Eunji ; Ohba, Masaaki ; Lee, Shim Sung ; Vittal, Jagadese J. / Metal Organo-Polymeric Framework via [2 + 2] Cycloaddition Reaction : Influence of Hydrogen Bonding on Depolymerization. In: Crystal Growth and Design. 2019 ; Vol. 19, No. 3. pp. 1996-2000.
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abstract = "In the doubly interpenetrated metal-organic framework (MOF) structure with cds topology, [Zn 2 (bpeb)(dhbdc)(fa) 2 ], 1 (where bpeb = trans,trans,trans-1,4-bis[2-(4′-pyridyl)ethenyl]benzene, dhbdc = 2,5-dihydroxy-benzene-1,4-dicarboxylate, and fa = formate), the adjacent bpeb ligands are aligned in a slip-stacked manner infinitely, and the olefin pairs are aligned in parallel ready to undergo a quantitative photochemical [2 + 2] cycloaddition reaction. The single-crystal-to-single-crystal (SCSC) photoreaction under UV light yielded a non-interpenetrated [Zn 2 (poly-bppcb)(dhbdc)(fa) 2 ], 2 (where poly-bppcb = 1,3-(4,4′-bipyridyl)-2-phenylcyclobutane) in which the poly-bppcb polymer comprising cyclobutane rings are nicely integrated into the two-dimensional coordination polymeric sheet formed by [Zn 2 (dhbdc)(fa) 2 ]. This organic polymer can be depolymerized back to 1 by heating 2 at 250 °C in a hot air oven for 6 h. The cleavage of cyclobutane rings to bpeb ligands has been attributed to the hydrogen bonding of the two hydroxy groups in the dhbdc ligand. In a similar metal organo-polymeric framework with bdc ligand, the poly-bppcb could not be depolymerized. Thus, this study provided some new insights into the reversible cleavage of cyclobutane polymers. These polymeric materials based on cyclobutane may be environmentally benign as these can be depolymerized to yield easily disposable and degradable monomers.",
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AB - In the doubly interpenetrated metal-organic framework (MOF) structure with cds topology, [Zn 2 (bpeb)(dhbdc)(fa) 2 ], 1 (where bpeb = trans,trans,trans-1,4-bis[2-(4′-pyridyl)ethenyl]benzene, dhbdc = 2,5-dihydroxy-benzene-1,4-dicarboxylate, and fa = formate), the adjacent bpeb ligands are aligned in a slip-stacked manner infinitely, and the olefin pairs are aligned in parallel ready to undergo a quantitative photochemical [2 + 2] cycloaddition reaction. The single-crystal-to-single-crystal (SCSC) photoreaction under UV light yielded a non-interpenetrated [Zn 2 (poly-bppcb)(dhbdc)(fa) 2 ], 2 (where poly-bppcb = 1,3-(4,4′-bipyridyl)-2-phenylcyclobutane) in which the poly-bppcb polymer comprising cyclobutane rings are nicely integrated into the two-dimensional coordination polymeric sheet formed by [Zn 2 (dhbdc)(fa) 2 ]. This organic polymer can be depolymerized back to 1 by heating 2 at 250 °C in a hot air oven for 6 h. The cleavage of cyclobutane rings to bpeb ligands has been attributed to the hydrogen bonding of the two hydroxy groups in the dhbdc ligand. In a similar metal organo-polymeric framework with bdc ligand, the poly-bppcb could not be depolymerized. Thus, this study provided some new insights into the reversible cleavage of cyclobutane polymers. These polymeric materials based on cyclobutane may be environmentally benign as these can be depolymerized to yield easily disposable and degradable monomers.

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