Lanthanide Antenna Amplifier Multiplies the Optical Sensing Efficiency in Phototautomeric Metal–Organic Frameworks DOI
Weijie Zhang,

Wen-Zhu Sun,

Ji-Tong Xu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

Metal-organic frameworks (MOFs) incorporating phototautomeric ligands have shown significant potential for new-generation optical sensing devices. It is challenging to enlarge the energy difference of tautomers, which crucial improving efficiency. Herein, we report a novel tactic amplify excited-state intramolecular proton transfer (ESIPT) effect via "antenna effect" in lanthanide sensitization. Specifically, by leveraging enol (E)-keto (K) phototautomerization process, achieve precise manipulation gap between lowest ligand triplet state and Eu(III) emitting level through fine-tuning. As result, small wavelength shift (10 nm) E* K* emissions amplified into an approximately 65-fold intensity change emission. This enhancement accompanied significantly lowered limit detection (LOD: 0.53 μg/L) improved sensitivity (0.6955% RH-1) real-time humidity monitoring across broad linear range (0-95.0% RH). Computational simulations single-crystal analyses demonstrate two key mechanisms: (1) appropriate hydrophilic/hydrophobic distribution MOF cavity facilitates rapid hydration/dehydration (2) H2O desorption/adsorption-dependent ESIPT switching governs deactivation/activation 4f excited state. work presents optimization approach enhance utilization MOF-based sensing.

Language: Английский

Plastic Pores for Switchable and Optimized Adsorption Behaviors DOI Creative Commons

Xuewen Zhang,

Ronghua Wang, Jie‐Peng Zhang

et al.

ACS Central Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Similar to conventional solids, porous materials have demonstrated rigid and flexible behaviors. Here, we show that pores can be not just elastic but also plastic. By variation of the hydrogen-bonding ability steric hindrance ligand side groups, energy difference barrier between metastable states a framework are fine-tuned enable plastic behavior. All pore structures transform target ones in atmospheres guests with sufficiently high pressures, all shaped remain unchanged after guest removal, resulting optimized host-guest recognitions for guests. Up 6-fold increase adsorption selectivity 9-fold purification productivity CO2 capture coalmine CH4 upgrading, even inversion CO2/C2H2 selectivity, been achieved by reversible pore-shaping single plastic-pore adsorbent. The realization creates an opportunity on-demand switching separation functions performances.

Language: Английский

Citations

0
Lanthanide Antenna Amplifier Multiplies the Optical Sensing Efficiency in Phototautomeric Metal–Organic Frameworks DOI
Weijie Zhang,

Wen-Zhu Sun,

Ji-Tong Xu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

Metal-organic frameworks (MOFs) incorporating phototautomeric ligands have shown significant potential for new-generation optical sensing devices. It is challenging to enlarge the energy difference of tautomers, which crucial improving efficiency. Herein, we report a novel tactic amplify excited-state intramolecular proton transfer (ESIPT) effect via "antenna effect" in lanthanide sensitization. Specifically, by leveraging enol (E)-keto (K) phototautomerization process, achieve precise manipulation gap between lowest ligand triplet state and Eu(III) emitting level through fine-tuning. As result, small wavelength shift (10 nm) E* K* emissions amplified into an approximately 65-fold intensity change emission. This enhancement accompanied significantly lowered limit detection (LOD: 0.53 μg/L) improved sensitivity (0.6955% RH-1) real-time humidity monitoring across broad linear range (0-95.0% RH). Computational simulations single-crystal analyses demonstrate two key mechanisms: (1) appropriate hydrophilic/hydrophobic distribution MOF cavity facilitates rapid hydration/dehydration (2) H2O desorption/adsorption-dependent ESIPT switching governs deactivation/activation 4f excited state. work presents optimization approach enhance utilization MOF-based sensing.

Language: Английский

Citations

0