DOI: 10.1002/chem.200401201. Synthesis, X‐ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle‐Wheel Motifs: Implications for Hydrogen Storage in Porous Materials

Synthesis, X‐ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle‐Wheel Motifs: Implications for Hydrogen Storage in Porous Materials

10.1002/chem.200401201

Crossref journal-article

Wiley

Chemistry – A European Journal (311)

Abstract

AbstractA systematic modulation of organic ligands connecting dinuclear paddle‐wheel motifs leads to a series of isomorphous metal‐organic porous materials that have a three‐dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4‐benzenedicarboxylate (1,4‐bdc), tetramethylterephthalate (tmbdc), 1,4‐naphthalenedicarboxylate (1,4‐ndc), tetrafluoroterephthalate (tfbdc), or 2,6‐naphthalenedicarboxylate (2,6‐ndc) are linear linkers that form two‐dimensional layers, and diamine ligands, 4‐diazabicyclo[2.2.2]octane (dabco) or 4,4′‐dipyridyl (bpy), coordinate at both sides of Zn2 paddle‐wheel units to bridge the layers vertically. The resulting open frameworks [Zn2(1,4‐bdc)2(dabco)] (1), [Zn2(1,4‐bdc)(tmbdc)(dabco)] (2), [Zn2(tmbdc)2(dabco)] (3), [Zn2(1,4‐ndc)2(dabco)] (4), [Zn2(tfbdc)2(dabco)] (5), and [Zn2(tmbdc)2(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4‐bdc derivatives. [Zn2(1,4‐bdc)2(bpy)] (6) and [Zn2(2,6‐ndc)2(bpy)] (7) have two‐ and threefold interpenetrating structures, respectively. The non‐interpenetrating frameworks (1–5 and 8) possess surface areas in the range of 1450–2090 m2g−1 and hydrogen sorption capacities of 1.7–2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.

Bibliography

Chun, H., Dybtsev, D. N., Kim, H., & Kim, K. (2005). Synthesis, Xâray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on PaddleâWheel Motifs: Implications for Hydrogen Storage in Porous Materials. Chemistry â A European Journal, 11(12), 3521â3529. Portico.

Authors 4

Hyungphil Chun (first)
Danil N. Dybtsev (additional)
Hyunuk Kim (additional)
Kimoon Kim (additional)

References 52 Referenced 825

10.1002/ange.200300610
10.1002/anie.200300610
10.1002/ange.200300588
10.1002/anie.200300588
10.1002/anie.200300636
10.1039/b200393g
10.1039/b305705b
10.1021/ar000034b
10.1021/ja981669x
10.1126/science.283.5405.1148
10.1038/46248
10.1126/science.1067208
10.1126/science.305.5686.958
10.1038/35104634
10.1002/ange.200460712
10.1002/anie.200460712
10.1002/ange.200353494
10.1002/anie.200353494
10.1021/ja049408c
10.1021/ja0392871
10.1021/ja038678c
10.1039/B308903G
10.1126/science.1083440
10.1021/ja028341v
10.1246/bcsj.71.1739
10.1021/cm011070n
10.1002/ange.200453923
10.1002/anie.200453923
10.1002/ejic.200300375
10.1021/ic049005d
10.1039/b211738j
K. Kim and co‐workers unpublished results.
10.1039/b108031h
The X‐ray structure analysis from a single crystal as‐synthesized is identical except for extensive disorder of guest molecules and is not reported here.
The SQUEEZE routine of PLATON returns only five unaccounted electrons per unit cell.
10.1039/b110899a
{'key': 'e_1_2_6_39_2', 'volume-title': 'Zeolite Molecular Sieves', 'author': 'Breck D. W.', 'year': '1974'} / Zeolite Molecular Sieves by Breck D. W. (1974)
10.1126/science.1101982
The measured uptake in cm3 g−1was converted to weight percent by multiplying by a factor of 0.009.
Assuming that monolayer condensation of hydrogen on a solid leads to a maximum 1.3×10−5mol m−2.[4b]
10.1021/la0355500
10.1021/nl0341281
10.1021/ja039215
A. L. Spek PLATON a multipurpose crystallographic tool Utrecht University Utrecht The Netherlands 2001.

Dates

Type	When
Created	20 years, 5 months ago (March 11, 2005, 8:03 a.m.)
Deposited	1 year, 10 months ago (Oct. 16, 2023, 3:38 p.m.)
Indexed	4 weeks, 1 day ago (July 23, 2025, 8:06 a.m.)
Issued	20 years, 2 months ago (May 30, 2005)
Published	20 years, 2 months ago (May 30, 2005)
Published Online	20 years, 2 months ago (May 30, 2005)
Published Print	20 years, 2 months ago (June 6, 2005)

Funders 0

None

BibTeX

@article{Chun_2005, title={Synthesis, X‐ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle‐Wheel Motifs: Implications for Hydrogen Storage in Porous Materials}, volume={11}, ISSN={1521-3765}, url={http://dx.doi.org/10.1002/chem.200401201}, DOI={10.1002/chem.200401201}, number={12}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Chun, Hyungphil and Dybtsev, Danil N. and Kim, Hyunuk and Kim, Kimoon}, year={2005}, month=may, pages={3521–3529} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        7,
        23
      ]
    ],
    "date-time": "2025-07-23T12:06:58Z",
    "timestamp": 1753272418086
  },
  "reference-count": 52,
  "publisher": "Wiley",
  "issue": "12",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2005,
            3,
            11
          ]
        ],
        "date-time": "2005-03-11T00:00:00Z",
        "timestamp": 1110499200000
      },
      "content-version": "vor",
      "delay-in-days": 0,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#vor"
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        2005,
        6,
        6
      ]
    ]
  },
  "abstract": "<jats:title>Abstract</jats:title><jats:p>A systematic modulation of organic ligands connecting dinuclear paddle\u2010wheel motifs leads to a series of isomorphous metal\u2010organic porous materials that have a three\u2010dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4\u2010benzenedicarboxylate (1,4\u2010bdc), tetramethylterephthalate (tmbdc), 1,4\u2010naphthalenedicarboxylate (1,4\u2010ndc), tetrafluoroterephthalate (tfbdc), or 2,6\u2010naphthalenedicarboxylate (2,6\u2010ndc) are linear linkers that form two\u2010dimensional layers, and diamine ligands, 4\u2010diazabicyclo[2.2.2]octane (dabco) or 4,4\u2032\u2010dipyridyl (bpy), coordinate at both sides of Zn<jats:sub>2</jats:sub> paddle\u2010wheel units to bridge the layers vertically. The resulting open frameworks [Zn<jats:sub>2</jats:sub>(1,4\u2010bdc)<jats:sub>2</jats:sub>(dabco)] (<jats:bold>1</jats:bold>), [Zn<jats:sub>2</jats:sub>(1,4\u2010bdc)(tmbdc)(dabco)] (<jats:bold>2</jats:bold>), [Zn<jats:sub>2</jats:sub>(tmbdc)<jats:sub>2</jats:sub>(dabco)] (<jats:bold>3</jats:bold>), [Zn<jats:sub>2</jats:sub>(1,4\u2010ndc)<jats:sub>2</jats:sub>(dabco)] (<jats:bold>4</jats:bold>), [Zn<jats:sub>2</jats:sub>(tfbdc)<jats:sub>2</jats:sub>(dabco)] (<jats:bold>5</jats:bold>), and [Zn<jats:sub>2</jats:sub>(tmbdc)<jats:sub>2</jats:sub>(bpy)] (<jats:bold>8</jats:bold>) possess varying size of pores and free apertures originating from the side groups of the 1,4\u2010bdc derivatives. [Zn<jats:sub>2</jats:sub>(1,4\u2010bdc)<jats:sub>2</jats:sub>(bpy)] (<jats:bold>6</jats:bold>) and [Zn<jats:sub>2</jats:sub>(2,6\u2010ndc)<jats:sub>2</jats:sub>(bpy)] (<jats:bold>7</jats:bold>) have two\u2010 and threefold interpenetrating structures, respectively. The non\u2010interpenetrating frameworks (<jats:bold>1</jats:bold>\u2013<jats:bold>5</jats:bold> and <jats:bold>8</jats:bold>) possess surface areas in the range of 1450\u20132090 m<jats:sup>2</jats:sup>g<jats:sup>\u22121</jats:sup> and hydrogen sorption capacities of 1.7\u20132.1 wt\u2009% at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.</jats:p>",
  "DOI": "10.1002/chem.200401201",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2005,
        3,
        11
      ]
    ],
    "date-time": "2005-03-11T13:03:20Z",
    "timestamp": 1110546200000
  },
  "page": "3521-3529",
  "source": "Crossref",
  "is-referenced-by-count": 825,
  "title": "Synthesis, X\u2010ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle\u2010Wheel Motifs: Implications for Hydrogen Storage in Porous Materials",
  "prefix": "10.1002",
  "volume": "11",
  "author": [
    {
      "given": "Hyungphil",
      "family": "Chun",
      "sequence": "first",
      "affiliation": []
    },
    {
      "given": "Danil N.",
      "family": "Dybtsev",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Hyunuk",
      "family": "Kim",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Kimoon",
      "family": "Kim",
      "sequence": "additional",
      "affiliation": []
    }
  ],
  "member": "311",
  "published-online": {
    "date-parts": [
      [
        2005,
        5,
        30
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_2_6_1_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.200300610"
    },
    {
      "key": "e_1_2_6_2_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.200300610"
    },
    {
      "key": "e_1_2_6_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.200300588"
    },
    {
      "key": "e_1_2_6_3_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.200300588"
    },
    {
      "key": "e_1_2_6_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.200300636"
    },
    {
      "key": "e_1_2_6_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b200393g"
    },
    {
      "key": "e_1_2_6_6_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b305705b"
    },
    {
      "key": "e_1_2_6_7_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ar000034b"
    },
    {
      "key": "e_1_2_6_8_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_9_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja981669x"
    },
    {
      "key": "e_1_2_6_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.283.5405.1148"
    },
    {
      "key": "e_1_2_6_11_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1038/46248"
    },
    {
      "key": "e_1_2_6_12_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.1067208"
    },
    {
      "key": "e_1_2_6_13_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_14_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.305.5686.958"
    },
    {
      "key": "e_1_2_6_15_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1038/35104634"
    },
    {
      "key": "e_1_2_6_16_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_17_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.200460712"
    },
    {
      "key": "e_1_2_6_17_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.200460712"
    },
    {
      "key": "e_1_2_6_18_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.200353494"
    },
    {
      "key": "e_1_2_6_18_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.200353494"
    },
    {
      "key": "e_1_2_6_19_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja049408c"
    },
    {
      "key": "e_1_2_6_20_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja0392871"
    },
    {
      "key": "e_1_2_6_21_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja038678c"
    },
    {
      "key": "e_1_2_6_22_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/B308903G"
    },
    {
      "key": "e_1_2_6_23_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.1083440"
    },
    {
      "key": "e_1_2_6_24_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja028341v"
    },
    {
      "key": "e_1_2_6_25_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_26_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1246/bcsj.71.1739"
    },
    {
      "key": "e_1_2_6_27_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cm011070n"
    },
    {
      "key": "e_1_2_6_28_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_29_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.200453923"
    },
    {
      "key": "e_1_2_6_29_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.200453923"
    },
    {
      "key": "e_1_2_6_30_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ejic.200300375"
    },
    {
      "key": "e_1_2_6_31_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_32_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic049005d"
    },
    {
      "key": "e_1_2_6_33_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b211738j"
    },
    {
      "key": "e_1_2_6_34_2",
      "unstructured": "K. Kim and co\u2010workers unpublished results."
    },
    {
      "key": "e_1_2_6_35_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b108031h"
    },
    {
      "key": "e_1_2_6_36_2",
      "unstructured": "The X\u2010ray structure analysis from a single crystal as\u2010synthesized is identical except for extensive disorder of guest molecules and is not reported here."
    },
    {
      "key": "e_1_2_6_37_2",
      "unstructured": "The SQUEEZE routine of PLATON returns only five unaccounted electrons per unit cell."
    },
    {
      "key": "e_1_2_6_38_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b110899a"
    },
    {
      "key": "e_1_2_6_39_2",
      "volume-title": "Zeolite Molecular Sieves",
      "author": "Breck D. W.",
      "year": "1974"
    },
    {
      "key": "e_1_2_6_40_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.1101982"
    },
    {
      "key": "e_1_2_6_41_2",
      "unstructured": "The measured uptake in cm3\u2009g\u22121was converted to weight percent by multiplying by a factor of 0.009."
    },
    {
      "key": "e_1_2_6_42_2",
      "unstructured": "Assuming that monolayer condensation of hydrogen on a solid leads to a maximum 1.3\u00d710\u22125mol\u2009m\u22122.[4b]"
    },
    {
      "key": "e_1_2_6_43_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/la0355500"
    },
    {
      "key": "e_1_2_6_44_2",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_6_45_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/nl0341281"
    },
    {
      "key": "e_1_2_6_46_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja039215"
    },
    {
      "key": "e_1_2_6_47_2",
      "unstructured": "A. L. Spek PLATON a multipurpose crystallographic tool Utrecht University Utrecht The Netherlands 2001."
    }
  ],
  "container-title": "Chemistry \u2013 A European Journal",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.200401201",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/full/10.1002/chem.200401201",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        10,
        16
      ]
    ],
    "date-time": "2023-10-16T19:38:41Z",
    "timestamp": 1697485121000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.200401201"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        2005,
        5,
        30
      ]
    ]
  },
  "references-count": 52,
  "journal-issue": {
    "issue": "12",
    "published-print": {
      "date-parts": [
        [
          2005,
          6,
          6
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1002/chem.200401201"
  ],
  "URL": "http://dx.doi.org/10.1002/chem.200401201",
  "relation": {},
  "ISSN": [
    "0947-6539",
    "1521-3765"
  ],
  "subject": [],
  "container-title-short": "Chemistry A European J",
  "published": {
    "date-parts": [
      [
        2005,
        5,
        30
      ]
    ]
  }
}