Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1

Wenhua Zhang; Olesia Kozachuk; Raghavender Medishetty; Andreas Schneemann; Ralph Wagner; Kira Khaletskaya; Konstantin Epp; Roland A. Fischer

doi:10.1002/ejic.201500478

Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1

Wenhua Zhang
, Olesia Kozachuk
, Raghavender Medishetty
, Andreas Schneemann
, Ralph Wagner
, Kira Khaletskaya
, Konstantin Epp
, Roland A. Fischer

Max-Planck-lnstitut für Kohlenforschung
Bergische Universität Wuppertal

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

27 Scopus citations

Abstract

A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru₃(BTC)₂X_x]·G_g (BTC = 1,3,5-benzenetricarboxylate; X = counter-anion, G = guest molecules) which are structural analogues of [M₃(BTC)₂] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru₂(OOCR)₄X] and [Ru₂(OOCCH₃)₄]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl^-) and weakly coordinating Y ([BF₄]^- or [BPh₄]^-) as well as the alkyl groups at the carboxylate ligand [R = CH₃ or C(CH₃)₃] were utilized. Four phase-pure Ru-MOFs were obtained: [Ru₃(BTC)₂Cl_0.5(OH)]·(AcOH)_1.5 (1), [Ru₃(BTC)₂Cl_1.2(OH)_0.3]·(H₃BTC)_0.15(AcOH)_2.4(PivOH)_0.45 (2), [Ru₃(BTC)₂F_0.5(OH)]·(AcOH)_1.0 (3) and [Ru₃(BTC)₂(OH)_1.5]·(H₃BTC)_0.5·(AcOH)_1.4 (4) {AcOH = CH₃COOH, PivOH = (CH₃)₃CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1-4, i.e. powder X-ray diffraction (PXRD), IR- and ¹H-NMR spectroscopy, thermal gravimetric analysis (TGA) and N₂ sorption were employed. The valence state of the Ru-sites were studied by X-ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work-up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru-MOF materials. A controlled secondary building unit approach (CSA) was employed to obtain a series of isostructural ruthenium metal-organic frameworks (MOFs) of the general formula [Ru₃(BTC)₂X_x]·G_g (BTC = 1,3,5-benzenetricarboxylate; X = counter anion, G = guest molecules) which are analogues of [Cu₃(BTC)₂] (HKUST-1).

Original language	English
Pages (from-to)	3913-3920
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2015
Issue number	23
DOIs	https://doi.org/10.1002/ejic.201500478
State	Published - 1 Aug 2015
Externally published	Yes

Keywords

Coordinatively unsaturated metal sites
Metal-organic frameworks
Ruthenium

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10.1002/ejic.201500478

Cite this

@article{f970d96f67e84218a9428864145596b3,

title = "Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1",

abstract = "A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter-anion, G = guest molecules) which are structural analogues of [M3(BTC)2] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru2(OOCR)4X] and [Ru2(OOCCH3)4]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl-) and weakly coordinating Y ([BF4]- or [BPh4]-) as well as the alkyl groups at the carboxylate ligand [R = CH3 or C(CH3)3] were utilized. Four phase-pure Ru-MOFs were obtained: [Ru3(BTC)2Cl0.5(OH)]·(AcOH)1.5 (1), [Ru3(BTC)2Cl1.2(OH)0.3]·(H3BTC)0.15(AcOH)2.4(PivOH)0.45 (2), [Ru3(BTC)2F0.5(OH)]·(AcOH)1.0 (3) and [Ru3(BTC)2(OH)1.5]·(H3BTC)0.5·(AcOH)1.4 (4) \{AcOH = CH3COOH, PivOH = (CH3)3CCOOH\}. The series of characterization data support the analytical composition and isostructural nature of 1-4, i.e. powder X-ray diffraction (PXRD), IR- and 1H-NMR spectroscopy, thermal gravimetric analysis (TGA) and N2 sorption were employed. The valence state of the Ru-sites were studied by X-ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work-up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru-MOF materials. A controlled secondary building unit approach (CSA) was employed to obtain a series of isostructural ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter anion, G = guest molecules) which are analogues of [Cu3(BTC)2] (HKUST-1).",

keywords = "Coordinatively unsaturated metal sites, Metal-organic frameworks, Ruthenium",

author = "Wenhua Zhang and Olesia Kozachuk and Raghavender Medishetty and Andreas Schneemann and Ralph Wagner and Kira Khaletskaya and Konstantin Epp and Fischer, \{Roland A.\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2015 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim.",

year = "2015",

month = aug,

day = "1",

doi = "10.1002/ejic.201500478",

language = "English",

volume = "2015",

pages = "3913--3920",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "23",

}

TY - JOUR

T1 - Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1

AU - Zhang, Wenhua

AU - Kozachuk, Olesia

AU - Medishetty, Raghavender

AU - Schneemann, Andreas

AU - Wagner, Ralph

AU - Khaletskaya, Kira

AU - Epp, Konstantin

AU - Fischer, Roland A.

PY - 2015/8/1

Y1 - 2015/8/1

N2 - A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter-anion, G = guest molecules) which are structural analogues of [M3(BTC)2] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru2(OOCR)4X] and [Ru2(OOCCH3)4]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl-) and weakly coordinating Y ([BF4]- or [BPh4]-) as well as the alkyl groups at the carboxylate ligand [R = CH3 or C(CH3)3] were utilized. Four phase-pure Ru-MOFs were obtained: [Ru3(BTC)2Cl0.5(OH)]·(AcOH)1.5 (1), [Ru3(BTC)2Cl1.2(OH)0.3]·(H3BTC)0.15(AcOH)2.4(PivOH)0.45 (2), [Ru3(BTC)2F0.5(OH)]·(AcOH)1.0 (3) and [Ru3(BTC)2(OH)1.5]·(H3BTC)0.5·(AcOH)1.4 (4) {AcOH = CH3COOH, PivOH = (CH3)3CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1-4, i.e. powder X-ray diffraction (PXRD), IR- and 1H-NMR spectroscopy, thermal gravimetric analysis (TGA) and N2 sorption were employed. The valence state of the Ru-sites were studied by X-ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work-up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru-MOF materials. A controlled secondary building unit approach (CSA) was employed to obtain a series of isostructural ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter anion, G = guest molecules) which are analogues of [Cu3(BTC)2] (HKUST-1).

AB - A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter-anion, G = guest molecules) which are structural analogues of [M3(BTC)2] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru2(OOCR)4X] and [Ru2(OOCCH3)4]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl-) and weakly coordinating Y ([BF4]- or [BPh4]-) as well as the alkyl groups at the carboxylate ligand [R = CH3 or C(CH3)3] were utilized. Four phase-pure Ru-MOFs were obtained: [Ru3(BTC)2Cl0.5(OH)]·(AcOH)1.5 (1), [Ru3(BTC)2Cl1.2(OH)0.3]·(H3BTC)0.15(AcOH)2.4(PivOH)0.45 (2), [Ru3(BTC)2F0.5(OH)]·(AcOH)1.0 (3) and [Ru3(BTC)2(OH)1.5]·(H3BTC)0.5·(AcOH)1.4 (4) {AcOH = CH3COOH, PivOH = (CH3)3CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1-4, i.e. powder X-ray diffraction (PXRD), IR- and 1H-NMR spectroscopy, thermal gravimetric analysis (TGA) and N2 sorption were employed. The valence state of the Ru-sites were studied by X-ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work-up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru-MOF materials. A controlled secondary building unit approach (CSA) was employed to obtain a series of isostructural ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter anion, G = guest molecules) which are analogues of [Cu3(BTC)2] (HKUST-1).

KW - Coordinatively unsaturated metal sites

KW - Metal-organic frameworks

KW - Ruthenium

UR - https://www.scopus.com/pages/publications/84939261297

U2 - 10.1002/ejic.201500478

DO - 10.1002/ejic.201500478

M3 - Article

AN - SCOPUS:84939261297

SN - 1434-1948

VL - 2015

SP - 3913

EP - 3920

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 23

ER -

Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1

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Keywords

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