Porous polyrotaxane coordination networks containing two distinct conformers of a discontinuously flexible ligand

Chris S. Hawes, Gregory P. Knowles, Alan L. Chaffee, Keith F. White, Brendan F. Abrahams, Stuart R. Batten, David R. Turner

Research output: Contribution to journalArticleResearchpeer-review

6 Citations (Scopus)

Abstract

A new divergent homopiperazine-derived ligand N,N′-bis(4-carboxyphenyl)-1,4-diazacycloheptane H2L has been prepared, containing a semirigid saturated heterocyclic core which is capable of providing multiple distinct bridging geometries. Reaction of H2L with zinc acetate in DMSO gives a two-dimensional parallel interpenetrated polyrotaxane structure 1 in which the loops and rods are formed by the bent cis-(eq,ax) twist boat and trans-(ax,ax) twist chair conformers, respectively. By matching the distances between the solvated metal sites in the structure of 1, a related material 2 can be prepared incorporating the pillaring ligand trans-1,2-bis(4-pyridyl)ethylene bpe. Compound 2 displays a similar polyrotaxane interpenetration mode, permitted by the presence of both cis and trans ligand conformers, but displays a three-dimensional 2.69 topology related to the dia diamondoid network. The guest exchange and gas adsorption properties of both materials were investigated; while compound 1 displays poor stability to guest exchange and negligible gas uptake, the higher connectivity microporous compound 2 shows facile guest exchange and a surprisingly high CO2 capacity of 12 wt % at 1 bar and 273 K, and a zero-loading enthalpy of adsorption of -32 kJ mol-1. High-pressure adsorption isotherms also show moderate physisorption of H2 and CH4 within the material.

Original languageEnglish
Pages (from-to)10467-10474
Number of pages8
JournalInorganic Chemistry
Volume55
Issue number20
DOIs
Publication statusPublished - 17 Oct 2016

Cite this

@article{6f97fe60048749fcba2cae9ba820194d,
title = "Porous polyrotaxane coordination networks containing two distinct conformers of a discontinuously flexible ligand",
abstract = "A new divergent homopiperazine-derived ligand N,N′-bis(4-carboxyphenyl)-1,4-diazacycloheptane H2L has been prepared, containing a semirigid saturated heterocyclic core which is capable of providing multiple distinct bridging geometries. Reaction of H2L with zinc acetate in DMSO gives a two-dimensional parallel interpenetrated polyrotaxane structure 1 in which the loops and rods are formed by the bent cis-(eq,ax) twist boat and trans-(ax,ax) twist chair conformers, respectively. By matching the distances between the solvated metal sites in the structure of 1, a related material 2 can be prepared incorporating the pillaring ligand trans-1,2-bis(4-pyridyl)ethylene bpe. Compound 2 displays a similar polyrotaxane interpenetration mode, permitted by the presence of both cis and trans ligand conformers, but displays a three-dimensional 2.69 topology related to the dia diamondoid network. The guest exchange and gas adsorption properties of both materials were investigated; while compound 1 displays poor stability to guest exchange and negligible gas uptake, the higher connectivity microporous compound 2 shows facile guest exchange and a surprisingly high CO2 capacity of 12 wt {\%} at 1 bar and 273 K, and a zero-loading enthalpy of adsorption of -32 kJ mol-1. High-pressure adsorption isotherms also show moderate physisorption of H2 and CH4 within the material.",
author = "Hawes, {Chris S.} and Knowles, {Gregory P.} and Chaffee, {Alan L.} and White, {Keith F.} and Abrahams, {Brendan F.} and Batten, {Stuart R.} and Turner, {David R.}",
year = "2016",
month = "10",
day = "17",
doi = "10.1021/acs.inorgchem.6b01713",
language = "English",
volume = "55",
pages = "10467--10474",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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Porous polyrotaxane coordination networks containing two distinct conformers of a discontinuously flexible ligand. / Hawes, Chris S.; Knowles, Gregory P.; Chaffee, Alan L.; White, Keith F.; Abrahams, Brendan F.; Batten, Stuart R.; Turner, David R.

In: Inorganic Chemistry, Vol. 55, No. 20, 17.10.2016, p. 10467-10474.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Porous polyrotaxane coordination networks containing two distinct conformers of a discontinuously flexible ligand

AU - Hawes, Chris S.

AU - Knowles, Gregory P.

AU - Chaffee, Alan L.

AU - White, Keith F.

AU - Abrahams, Brendan F.

AU - Batten, Stuart R.

AU - Turner, David R.

PY - 2016/10/17

Y1 - 2016/10/17

N2 - A new divergent homopiperazine-derived ligand N,N′-bis(4-carboxyphenyl)-1,4-diazacycloheptane H2L has been prepared, containing a semirigid saturated heterocyclic core which is capable of providing multiple distinct bridging geometries. Reaction of H2L with zinc acetate in DMSO gives a two-dimensional parallel interpenetrated polyrotaxane structure 1 in which the loops and rods are formed by the bent cis-(eq,ax) twist boat and trans-(ax,ax) twist chair conformers, respectively. By matching the distances between the solvated metal sites in the structure of 1, a related material 2 can be prepared incorporating the pillaring ligand trans-1,2-bis(4-pyridyl)ethylene bpe. Compound 2 displays a similar polyrotaxane interpenetration mode, permitted by the presence of both cis and trans ligand conformers, but displays a three-dimensional 2.69 topology related to the dia diamondoid network. The guest exchange and gas adsorption properties of both materials were investigated; while compound 1 displays poor stability to guest exchange and negligible gas uptake, the higher connectivity microporous compound 2 shows facile guest exchange and a surprisingly high CO2 capacity of 12 wt % at 1 bar and 273 K, and a zero-loading enthalpy of adsorption of -32 kJ mol-1. High-pressure adsorption isotherms also show moderate physisorption of H2 and CH4 within the material.

AB - A new divergent homopiperazine-derived ligand N,N′-bis(4-carboxyphenyl)-1,4-diazacycloheptane H2L has been prepared, containing a semirigid saturated heterocyclic core which is capable of providing multiple distinct bridging geometries. Reaction of H2L with zinc acetate in DMSO gives a two-dimensional parallel interpenetrated polyrotaxane structure 1 in which the loops and rods are formed by the bent cis-(eq,ax) twist boat and trans-(ax,ax) twist chair conformers, respectively. By matching the distances between the solvated metal sites in the structure of 1, a related material 2 can be prepared incorporating the pillaring ligand trans-1,2-bis(4-pyridyl)ethylene bpe. Compound 2 displays a similar polyrotaxane interpenetration mode, permitted by the presence of both cis and trans ligand conformers, but displays a three-dimensional 2.69 topology related to the dia diamondoid network. The guest exchange and gas adsorption properties of both materials were investigated; while compound 1 displays poor stability to guest exchange and negligible gas uptake, the higher connectivity microporous compound 2 shows facile guest exchange and a surprisingly high CO2 capacity of 12 wt % at 1 bar and 273 K, and a zero-loading enthalpy of adsorption of -32 kJ mol-1. High-pressure adsorption isotherms also show moderate physisorption of H2 and CH4 within the material.

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UR - http://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.6b01713

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VL - 55

SP - 10467

EP - 10474

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -