Research output: Contribution to journal › Article › peer-review
Radical-Doped Metal-Organic Framework : Route to Nanoscale Defects and Magnetostructural Functionalities. / Poryvaev, Artem S.; Polyukhov, Daniil M.; Gjuzi, Eva et al.
In: Inorganic Chemistry, Vol. 58, No. 13, 01.07.2019, p. 8471-8479.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Radical-Doped Metal-Organic Framework
T2 - Route to Nanoscale Defects and Magnetostructural Functionalities
AU - Poryvaev, Artem S.
AU - Polyukhov, Daniil M.
AU - Gjuzi, Eva
AU - Hoffmann, Frank
AU - Fröba, Michael
AU - Fedin, Matvey V.
N1 - Publisher Copyright: © 2019 American Chemical Society.
PY - 2019/7/1
Y1 - 2019/7/1
N2 - Nanosized structural defects in metal-organic frameworks (MOFs) attract growing attention and often remarkably enhance functional properties of these materials for various applications. In this work, a series of MOFs [Cu2(TPTA)1-x(BDPBTR)x] (H4TPTA, [1,1′:3′,1″-terphenyl]-3,3′′,5,5′′-tetracarboxylic acid; H4BDPBTR, 1,3-bis(3,5-dicarboxyphenyl)-1,2,4-benzotriazin-4-yl radical)) with a new stable radical linker doped into the structure has been synthesized and investigated using Electron Paramagnetic Resonance (EPR). Mixed linkers H4TPTA and H4BDPBTR were used to bridge copper(II) paddle-wheel units into a porous framework, where H4BDPBTR is the close structural analogue of H4TPTA. MOFs with various x = 0-0.4 were investigated. EPR studies indicated that the radical linker binds to the copper(II) units differently compared to diamagnetic linker, resulting in the formation of nanosized structural defects. Moreover, remarkable kinetic phenomena were observed upon cooling of this MOF, where slow structural rearrangements and concomitant changes of magnetic interactions were induced. Thus, our findings demonstrate that doping of structurally mimicking radical linkers into MOFs represents an efficient approach for designing target nanosized defects and introducing new magnetostructural functionalities for a variety of applications.
AB - Nanosized structural defects in metal-organic frameworks (MOFs) attract growing attention and often remarkably enhance functional properties of these materials for various applications. In this work, a series of MOFs [Cu2(TPTA)1-x(BDPBTR)x] (H4TPTA, [1,1′:3′,1″-terphenyl]-3,3′′,5,5′′-tetracarboxylic acid; H4BDPBTR, 1,3-bis(3,5-dicarboxyphenyl)-1,2,4-benzotriazin-4-yl radical)) with a new stable radical linker doped into the structure has been synthesized and investigated using Electron Paramagnetic Resonance (EPR). Mixed linkers H4TPTA and H4BDPBTR were used to bridge copper(II) paddle-wheel units into a porous framework, where H4BDPBTR is the close structural analogue of H4TPTA. MOFs with various x = 0-0.4 were investigated. EPR studies indicated that the radical linker binds to the copper(II) units differently compared to diamagnetic linker, resulting in the formation of nanosized structural defects. Moreover, remarkable kinetic phenomena were observed upon cooling of this MOF, where slow structural rearrangements and concomitant changes of magnetic interactions were induced. Thus, our findings demonstrate that doping of structurally mimicking radical linkers into MOFs represents an efficient approach for designing target nanosized defects and introducing new magnetostructural functionalities for a variety of applications.
KW - ELECTRON-PARAMAGNETIC-RESONANCE
KW - GAS-ADSORPTION
KW - AEROBIC OXIDATION
KW - CUPRIC IONS
KW - DERIVATIVES
KW - MIL-53
KW - EPR
KW - SPECTROSCOPY
KW - BEHAVIOR
KW - LINKER
UR - http://www.scopus.com/inward/record.url?scp=85067941747&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b00696
DO - 10.1021/acs.inorgchem.9b00696
M3 - Article
C2 - 31184867
AN - SCOPUS:85067941747
VL - 58
SP - 8471
EP - 8479
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 13
ER -
ID: 20709880