TY - JOUR
T1 - Light and Guest Responsive Behavior in a Porous Coordination Network Enabled by Reversible [2+2] Photocycloaddition
AU - Gao, Mei Yan
AU - Liu, Lunjie
AU - Deng, Chenghua
AU - Bon, Volodymyr
AU - Song, Bai Qiao
AU - Yang, Sihai
AU - Schröder, Martin
AU - Kaskel, Stefan
AU - Zaworotko, Michael J.
N1 - Publisher Copyright:
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2024/8/19
Y1 - 2024/8/19
N2 - Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation. Whereas reports on guest or light-responsive sorbents have increased in recent years, we are unaware of reports on sorbents that exhibit both light and guest-induced structural transformations. Herein, we report that the square lattice, sql, topology coordination network Zn(fba)(bis) ⋅ 2DMF (sql-5,6-Zn-α, 5=trans-4,4′-bis(1-imidazolyl)stilbene=bis, 6=2,2-bis(4-carboxyphenyl)hexafluoropropane=H2fba) underwent single-crystal-to-single-crystal transformation (SCSC) upon activation, affording nonporous sql-5,6-Zn-β. Parallel alignment at 3.23 Å of olefinic moieties on adjacent bis ligands in sql-5,6-Zn-α enabled SCSC [2+2] photocycloaddition upon exposure to UV light (365 nm) or sunlight. sql-5,6-Zn-α thereby transformed to mot-5,6-Zn-α, which was subsequently activated to the narrow pore phase mot-5,6-Zn-β. sql-5,6-Zn-β and mot-5,6-Zn-β both exhibited S-shaped adsorption isotherms characteristic of guest-induced structural changes when exposed to CO2 at 195 K (type-F–IV and type F–I, respectively). Cycling experiments conducted upon sql-5,6-Zn-β reduced particle size after cycle 1 and induced transformation into a rare example of a shape memory coordination network, sql-5,6-Zn-γ. Insight into this smorgasbord of SCSC phase changes was gained from in situ PXRD, single crystal XRD and 1H NMR spectroscopy experiments.
AB - Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation. Whereas reports on guest or light-responsive sorbents have increased in recent years, we are unaware of reports on sorbents that exhibit both light and guest-induced structural transformations. Herein, we report that the square lattice, sql, topology coordination network Zn(fba)(bis) ⋅ 2DMF (sql-5,6-Zn-α, 5=trans-4,4′-bis(1-imidazolyl)stilbene=bis, 6=2,2-bis(4-carboxyphenyl)hexafluoropropane=H2fba) underwent single-crystal-to-single-crystal transformation (SCSC) upon activation, affording nonporous sql-5,6-Zn-β. Parallel alignment at 3.23 Å of olefinic moieties on adjacent bis ligands in sql-5,6-Zn-α enabled SCSC [2+2] photocycloaddition upon exposure to UV light (365 nm) or sunlight. sql-5,6-Zn-α thereby transformed to mot-5,6-Zn-α, which was subsequently activated to the narrow pore phase mot-5,6-Zn-β. sql-5,6-Zn-β and mot-5,6-Zn-β both exhibited S-shaped adsorption isotherms characteristic of guest-induced structural changes when exposed to CO2 at 195 K (type-F–IV and type F–I, respectively). Cycling experiments conducted upon sql-5,6-Zn-β reduced particle size after cycle 1 and induced transformation into a rare example of a shape memory coordination network, sql-5,6-Zn-γ. Insight into this smorgasbord of SCSC phase changes was gained from in situ PXRD, single crystal XRD and 1H NMR spectroscopy experiments.
KW - flexibility
KW - photocycloaddition
KW - porous coordination networks
KW - shape memory
KW - single-crystal-to-single-crystal transformation
UR - http://www.scopus.com/inward/record.url?scp=85199341977&partnerID=8YFLogxK
U2 - 10.1002/anie.202404084
DO - 10.1002/anie.202404084
M3 - Article
AN - SCOPUS:85199341977
SN - 1433-7851
VL - 63
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 34
M1 - e202404084
ER -