Details
| Original language | English |
|---|---|
| Pages (from-to) | 6979-6985 |
| Number of pages | 7 |
| Journal | Chemistry - a European journal |
| Volume | 18 |
| Issue number | 22 |
| Publication status | Published - 16 Apr 2012 |
Abstract
Cycloaddition reactions are highly attractive for post-synthetic modification of metal-organic frameworks (MOFs). We report herein on cycloaddition reactions with PIZOF(R 1,R 2)s, which are porous interpenetrated Zr-based MOFs with Zr 6O 4(OH) 4(CO 2) 12 as the nodes and the dicarboxylates -O 2C[PE-P(R 1,R 2)-EP]CO 2 - (P: phenylene, E: ethynylene; R 1, R 2: side chains at the central phenylene unit) as the linkers. 1,3-Dipolar cycloaddition between the pendant ethyne moieties of PIZOF(OMe,OCH 2C≡CH) and 4-methylbenzyl azide resulted in 98 % conversion of the ethyne groups. Reactions of PIZOF(OMe,O(CH 2) 3furan) with maleimide, N-methylmaleimide, and N-phenylmaleimide converted 98, 99, and 89 % of the furan moieties into the Diels-Alder adducts. However, no reaction occurred with maleic anhydride. High-resolution 1H NMR spectra were crucial in determining the conversion and identifying the reaction products. Of all the reagents (NaOD/D 2O, D 2SO 4, Bu 4NF, CsF, CsF/DCl, and KHF 2) tested for the disassembly of the PIZOFs in [D 6]DMSO, the combination of CsF and DCl was found to be the best. The disassembly at room temperature was fast (5-15 min), and after the addition of K 2CO 3 the 1H NMR data were identical to those of the diacids (=protonated linkers) dissolved in pure DMSO. This allowed for simple structure elucidation through data comparison. CsF/DCl dissolves not only PIZOFs but also the hydrolytically very stable UiO-66.
Keywords
- cycloaddition, Diels-Alder reaction, metal-organic frameworks, post-synthetic modification, zirconium
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - a European journal, Vol. 18, No. 22, 16.04.2012, p. 6979-6985.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Post-synthetic modification of Zr-metal-organic frameworks through cycloaddition reactions
AU - Roy, Pascal
AU - Schaate, Andreas
AU - Behrens, Peter
AU - Godt, Adelheid
PY - 2012/4/16
Y1 - 2012/4/16
N2 - Cycloaddition reactions are highly attractive for post-synthetic modification of metal-organic frameworks (MOFs). We report herein on cycloaddition reactions with PIZOF(R 1,R 2)s, which are porous interpenetrated Zr-based MOFs with Zr 6O 4(OH) 4(CO 2) 12 as the nodes and the dicarboxylates -O 2C[PE-P(R 1,R 2)-EP]CO 2 - (P: phenylene, E: ethynylene; R 1, R 2: side chains at the central phenylene unit) as the linkers. 1,3-Dipolar cycloaddition between the pendant ethyne moieties of PIZOF(OMe,OCH 2C≡CH) and 4-methylbenzyl azide resulted in 98 % conversion of the ethyne groups. Reactions of PIZOF(OMe,O(CH 2) 3furan) with maleimide, N-methylmaleimide, and N-phenylmaleimide converted 98, 99, and 89 % of the furan moieties into the Diels-Alder adducts. However, no reaction occurred with maleic anhydride. High-resolution 1H NMR spectra were crucial in determining the conversion and identifying the reaction products. Of all the reagents (NaOD/D 2O, D 2SO 4, Bu 4NF, CsF, CsF/DCl, and KHF 2) tested for the disassembly of the PIZOFs in [D 6]DMSO, the combination of CsF and DCl was found to be the best. The disassembly at room temperature was fast (5-15 min), and after the addition of K 2CO 3 the 1H NMR data were identical to those of the diacids (=protonated linkers) dissolved in pure DMSO. This allowed for simple structure elucidation through data comparison. CsF/DCl dissolves not only PIZOFs but also the hydrolytically very stable UiO-66.
AB - Cycloaddition reactions are highly attractive for post-synthetic modification of metal-organic frameworks (MOFs). We report herein on cycloaddition reactions with PIZOF(R 1,R 2)s, which are porous interpenetrated Zr-based MOFs with Zr 6O 4(OH) 4(CO 2) 12 as the nodes and the dicarboxylates -O 2C[PE-P(R 1,R 2)-EP]CO 2 - (P: phenylene, E: ethynylene; R 1, R 2: side chains at the central phenylene unit) as the linkers. 1,3-Dipolar cycloaddition between the pendant ethyne moieties of PIZOF(OMe,OCH 2C≡CH) and 4-methylbenzyl azide resulted in 98 % conversion of the ethyne groups. Reactions of PIZOF(OMe,O(CH 2) 3furan) with maleimide, N-methylmaleimide, and N-phenylmaleimide converted 98, 99, and 89 % of the furan moieties into the Diels-Alder adducts. However, no reaction occurred with maleic anhydride. High-resolution 1H NMR spectra were crucial in determining the conversion and identifying the reaction products. Of all the reagents (NaOD/D 2O, D 2SO 4, Bu 4NF, CsF, CsF/DCl, and KHF 2) tested for the disassembly of the PIZOFs in [D 6]DMSO, the combination of CsF and DCl was found to be the best. The disassembly at room temperature was fast (5-15 min), and after the addition of K 2CO 3 the 1H NMR data were identical to those of the diacids (=protonated linkers) dissolved in pure DMSO. This allowed for simple structure elucidation through data comparison. CsF/DCl dissolves not only PIZOFs but also the hydrolytically very stable UiO-66.
KW - cycloaddition
KW - Diels-Alder reaction
KW - metal-organic frameworks
KW - post-synthetic modification
KW - zirconium
UR - http://www.scopus.com/inward/record.url?scp=84861549053&partnerID=8YFLogxK
U2 - 10.1002/chem.201103288
DO - 10.1002/chem.201103288
M3 - Article
AN - SCOPUS:84861549053
VL - 18
SP - 6979
EP - 6985
JO - Chemistry - a European journal
JF - Chemistry - a European journal
SN - 0947-6539
IS - 22
ER -