TY - JOUR
T1 - Modulation of the Dynamics of a Two-Dimensional Interweaving Metal-Organic Framework through Induced Hydrogen Bonding
AU - Fernández-Seriñán, Pilar
AU - Roztocki, K.
AU - Safarifard, Vahid
AU - Guillerm, Vincent
AU - Rodríguez-Hermida, Sabina
AU - Juanhuix, Judith
AU - Imaz, Inhar
AU - Morsali, Ali
AU - Maspoch Comamala, Daniel
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/3/25
Y1 - 2024/3/25
N2 - Inducing, understanding, and controlling the flexibility in metal-organic frameworks (MOFs) are of utmost interest due to the potential applications of dynamic materials in gas-related technologies. Herein, we report the synthesis of two isostructural two-dimensional (2D) interweaving zinc(II) MOFs, TMU-27 [Zn(bpipa)(bdc)] and TMU-27-NH [Zn(bpipa)(NH-bdc)], based on N,N'-bis-4-pyridyl-isophthalamide (bpipa) and 1,4-benzenedicarboxylate (bdc) or 2-amino-1,4-benzenedicarboxylate (NH-bdc), respectively. These frameworks differ only by the substitution at the meta-position of their respective bdc groups: an H atom in TMU-27 vs an NH group in TMU-27-NH. This difference strongly influences their respective responses to external stimuli, since we observed that the structure of TMU-27 changed due to desolvation and adsorption, whereas TMU-27-NH remained rigid. Using single-crystal X-ray diffraction and CO-sorption measurements, we discovered that upon CO sorption, TMU-27 undergoes a transition from a closed-pore phase to an open-pore phase. In contrast, we attributed the rigidification in TMU-27-NH to intermolecular hydrogen bonding between interweaving layers, namely, between the H atoms from the bdc-amino groups and the O atoms from the bpipa-amide groups within these layers. Additionally, by using scanning electron microscopy to monitor the CO adsorption and desorption in TMU-27, we were able to establish a correlation between the crystal size of this MOF and its transformation pressure.
AB - Inducing, understanding, and controlling the flexibility in metal-organic frameworks (MOFs) are of utmost interest due to the potential applications of dynamic materials in gas-related technologies. Herein, we report the synthesis of two isostructural two-dimensional (2D) interweaving zinc(II) MOFs, TMU-27 [Zn(bpipa)(bdc)] and TMU-27-NH [Zn(bpipa)(NH-bdc)], based on N,N'-bis-4-pyridyl-isophthalamide (bpipa) and 1,4-benzenedicarboxylate (bdc) or 2-amino-1,4-benzenedicarboxylate (NH-bdc), respectively. These frameworks differ only by the substitution at the meta-position of their respective bdc groups: an H atom in TMU-27 vs an NH group in TMU-27-NH. This difference strongly influences their respective responses to external stimuli, since we observed that the structure of TMU-27 changed due to desolvation and adsorption, whereas TMU-27-NH remained rigid. Using single-crystal X-ray diffraction and CO-sorption measurements, we discovered that upon CO sorption, TMU-27 undergoes a transition from a closed-pore phase to an open-pore phase. In contrast, we attributed the rigidification in TMU-27-NH to intermolecular hydrogen bonding between interweaving layers, namely, between the H atoms from the bdc-amino groups and the O atoms from the bpipa-amide groups within these layers. Additionally, by using scanning electron microscopy to monitor the CO adsorption and desorption in TMU-27, we were able to establish a correlation between the crystal size of this MOF and its transformation pressure.
KW - Benzenedicarboxylate
KW - Dynamic materials
KW - External stimulus
KW - Isostructural
KW - Meta positions
KW - Metalorganic frameworks (MOFs)
KW - Pore phase
KW - Pyridyl
KW - Two-dimensional
KW - Zinc metal
KW - Mil-53
KW - Structural transition
KW - Storage
KW - Adsorption
KW - Carbon-dioxide capture
UR - http://www.scopus.com/inward/record.url?scp=85187992370&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/165617b4-19c1-3396-85f6-dd3c199531eb/
U2 - 10.1021/acs.inorgchem.3c04522
DO - 10.1021/acs.inorgchem.3c04522
M3 - Article
C2 - 38484385
SN - 0020-1669
VL - 63
SP - 5552
EP - 5558
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 12
ER -