Expanded sodalite-type metal-organic frameworks: Increased stability and H2 adsorption through ligand-directed catenation

Mircea Dincǎ; Anne Dailly; Charlene Tsay; Jeffrey R. Long

doi:10.1021/ic701917w

Expanded sodalite-type metal-organic frameworks: Increased stability and H₂ adsorption through ligand-directed catenation

Mircea Dincǎ, Anne Dailly, Charlene Tsay, Jeffrey R. Long

Research output: Contribution to journal › Article › peer-review

182 Scopus citations

Abstract

The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H₃TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)-phenyl-s-triazine (H ₃TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H₃TPB-3tz with CuCl₂·2H₂O affords the noncatenated compound Cu₃[(Cu₄-Cl) ₃(TPB-3tz)₈]₂·11CuCl₂· 8H₂O·120DMF (2), while the reaction of H₃TPT-3tz with MnCl₂·4H₂O or CuCl₂·2H ₂0 generates the catenated compounds Mn₃[(Mn ₄Cl)₃(TPT-3tz)₈]₂·25H ₂O·15CH₃OH·95DMF (3) and Cu ₃[(Cu₄Cl)₃(TPT-3tz)₈] ₂·xsolvent (4). Significantly, catenation helps to stabilize the framework toward collapse upon desolvation, leading to an increase in the surface area from 1120 to 1580 m²/g and an increase in the hydrogen storage capacity from 2.8 to 3.7 excess wt % at 77 K for 2 and 3, respectively. The total hydrogen uptake in desolvated 3 reaches 4.5 wt % and 37 g/L at 80 bar and 77 K, demonstrating that control of catenation can be an important factor in the generation of hydrogen storage materials.

Original language	English (US)
Pages (from-to)	11-13
Number of pages	3
Journal	Inorganic Chemistry
Volume	47
Issue number	1
DOIs	https://doi.org/10.1021/ic701917w
State	Published - Jan 7 2008
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic701917w

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@article{8929e9a254fe4a3682523b6d205dcd02,

title = "Expanded sodalite-type metal-organic frameworks: Increased stability and H2 adsorption through ligand-directed catenation",

abstract = "The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H3TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)-phenyl-s-triazine (H 3TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H3TPB-3tz with CuCl2·2H2O affords the noncatenated compound Cu3[(Cu4-Cl) 3(TPB-3tz)8]2·11CuCl2· 8H2O·120DMF (2), while the reaction of H3TPT-3tz with MnCl2·4H2O or CuCl2·2H 20 generates the catenated compounds Mn3[(Mn 4Cl)3(TPT-3tz)8]2·25H 2O·15CH3OH·95DMF (3) and Cu 3[(Cu4Cl)3(TPT-3tz)8] 2·xsolvent (4). Significantly, catenation helps to stabilize the framework toward collapse upon desolvation, leading to an increase in the surface area from 1120 to 1580 m2/g and an increase in the hydrogen storage capacity from 2.8 to 3.7 excess wt \% at 77 K for 2 and 3, respectively. The total hydrogen uptake in desolvated 3 reaches 4.5 wt \% and 37 g/L at 80 bar and 77 K, demonstrating that control of catenation can be an important factor in the generation of hydrogen storage materials.",

author = "Mircea Dincǎ and Anne Dailly and Charlene Tsay and Long, \{Jeffrey R.\}",

year = "2008",

month = jan,

day = "7",

doi = "10.1021/ic701917w",

language = "English (US)",

volume = "47",

pages = "11--13",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Expanded sodalite-type metal-organic frameworks

T2 - Increased stability and H2 adsorption through ligand-directed catenation

AU - Dincǎ, Mircea

AU - Dailly, Anne

AU - Tsay, Charlene

AU - Long, Jeffrey R.

PY - 2008/1/7

Y1 - 2008/1/7

N2 - The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H3TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)-phenyl-s-triazine (H 3TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H3TPB-3tz with CuCl2·2H2O affords the noncatenated compound Cu3[(Cu4-Cl) 3(TPB-3tz)8]2·11CuCl2· 8H2O·120DMF (2), while the reaction of H3TPT-3tz with MnCl2·4H2O or CuCl2·2H 20 generates the catenated compounds Mn3[(Mn 4Cl)3(TPT-3tz)8]2·25H 2O·15CH3OH·95DMF (3) and Cu 3[(Cu4Cl)3(TPT-3tz)8] 2·xsolvent (4). Significantly, catenation helps to stabilize the framework toward collapse upon desolvation, leading to an increase in the surface area from 1120 to 1580 m2/g and an increase in the hydrogen storage capacity from 2.8 to 3.7 excess wt % at 77 K for 2 and 3, respectively. The total hydrogen uptake in desolvated 3 reaches 4.5 wt % and 37 g/L at 80 bar and 77 K, demonstrating that control of catenation can be an important factor in the generation of hydrogen storage materials.

AB - The torsion between the central benzene ring and the outer aromatic rings in 1,3,5-tri-p-(tetrazol-5-yl)phenylbenzene (H3TPB-3tz) and the absence of such strain in 2,4,6-tri-p-(tetrazol-5-yl)-phenyl-s-triazine (H 3TPT-3tz) are shown to allow the selective synthesis of noncatenated and catenated versions of expanded sodalite-type metal-organic frameworks. The reaction of H3TPB-3tz with CuCl2·2H2O affords the noncatenated compound Cu3[(Cu4-Cl) 3(TPB-3tz)8]2·11CuCl2· 8H2O·120DMF (2), while the reaction of H3TPT-3tz with MnCl2·4H2O or CuCl2·2H 20 generates the catenated compounds Mn3[(Mn 4Cl)3(TPT-3tz)8]2·25H 2O·15CH3OH·95DMF (3) and Cu 3[(Cu4Cl)3(TPT-3tz)8] 2·xsolvent (4). Significantly, catenation helps to stabilize the framework toward collapse upon desolvation, leading to an increase in the surface area from 1120 to 1580 m2/g and an increase in the hydrogen storage capacity from 2.8 to 3.7 excess wt % at 77 K for 2 and 3, respectively. The total hydrogen uptake in desolvated 3 reaches 4.5 wt % and 37 g/L at 80 bar and 77 K, demonstrating that control of catenation can be an important factor in the generation of hydrogen storage materials.

UR - https://www.scopus.com/pages/publications/38749151023

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U2 - 10.1021/ic701917w

DO - 10.1021/ic701917w

M3 - Article

C2 - 18067285

AN - SCOPUS:38749151023

SN - 0020-1669

VL - 47

SP - 11

EP - 13

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 1

ER -

Expanded sodalite-type metal-organic frameworks: Increased stability and H₂ adsorption through ligand-directed catenation

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