Beyond Molecular Design: Cocrystallization in Hydrogen-Bonded Organic Frameworks for Energy-Conserving Dehydration and Real-Time Luminescent Humidity Detection

Abstract

Luminescent probes attract increasing attentions for the unique superiorities like visually real-time detecting. However, for optical humidity sensing, it is still quite challenging to attain facile dehydration/activation in sensing materials, due to the high polarity of water molecules, which limits their applications in real-time detection and energy-conserving applications. Here, we report two fluorescent hydrogen-bonded organic frameworks (HOFs), HPISF-H₂O and TPISF. HPISF-H₂O achieves water absorption in low humidity, but needs an energy-intensive step (heating to ∼92°C in air) to dehydrate. Conversely, despite only a hydroxyl group being replaced, TPISF cannot bind to H₂O at all. In other words, real-time detection is not readily achieved through straightforward molecular design. Therefore, we propose a cocrystallization strategy to adjust their water-binding capacity. As a result, the HOF cocrystals are adjusted to have both good H₂O absorptivity and very gentle desorbing operation without heating (dry gas blowing or vacuuming). Benefiting from this strategy, appreciable advantages for an effective humidity sensor are realized, including real-time detection (second-scale response/recovery) and distinguishing fluorescence variation. Efficient sensing across a broad relative humidity (RH) range (10.0%–80.0%) was further achieved. Moreover, the mechanistic insight of fluorescent sensing was ascertained through detailed analyses of structural transformation, spectroscopic data, and theoretical approach.

Keywords

cocrystallization / energy-conserving materials / hydrogen-bonded organic framework / optical humidity detection / water-absorbing capacity

References

[1] (a) D. H. Park, B. J. Park, and J. M. Kim, “Hydrochromic Approaches to Mapping Human Sweat Pores,” Accounts of Chemical Research 49 (2016): 1211-1222. (b) Q. Zhang, D. Jiang, C. Xu, et al., “Wearable Electrochemical Biosensor Based on Molecularly Imprinted Ag Nanowires for Noninvasive Monitoring Lactate in Human Sweat,” Sensors and Actuators B: Chemical 320 (2020): 128325.

[2] (a) H. Moustafa, M. H. Hemida, M. A. Shemis, A. Dufresne, and M. Morsy, “Functionalized GO Nanoplatelets With Folic Acid as a Novel Material for Boosting Humidity Sensing of Chitosan/PVA Nanocomposites for Active Food Packaging,” Surfaces and Interfaces 41 (2023): 103229. (b) K. K. Gaikwad, S. Singh, and A. Ajji, “Moisture Absorbers for Food Packaging Applications,” Environmental Chemistry Letters 17 (2019): 609-628.

[3] C. Xue, S. X. Zhang, F. L. Zeng, H. Dong, S. H. Ma, and Y. H. Luo, “In Situ All-Weather Humidity Visualization by Using a Hydrophilic Sponge,” Advanced Materials Technologies 8 (2023): 2201188.

[4] S. Gopalakrishnan, J. Waimin, A. Zareei, et al., “A Biodegradable Chipless Sensor for Wireless Subsoil Health Monitoring,” Scientific Reports 12 (2022): 8011.

[5] (a) J. Wei, Y. Ma, C. Liu, et al., “Dynamic Tuning of Metal-Ligand Coordination Through Water Molecules to Induce Multicolor Fluorescence Variations for Humidity Monitoring and Anti-Counterfeiting Applications,” Journal of Materials Chemistry C 9 (2021): 5945-5951. (b) X. Chen, C. Hu, Y. Wang, et al., “A Self-Assemble Supramolecular Film With Humidity Visualization Enabled by Clusteroluminescence,” Advancement of Science 11 (2024): e2304946. (c) B. Li, Y. Zhang, J. Wang, et al., “Fast and Reversibly Humidity-Responsive Fluorescence Based on AIEgen Proton Transfer,” ACS Applied Materials & Interfaces 14 (2022): 49119. (d) F. Tan, L. Zha, and Q. Zhou, “Assembly of AIEgen-Based Fluorescent Metal–Organic Framework Nanosheets and Seaweed Cellulose Nanofibrils for Humidity Sensing and UV-Shielding,” Advanced Materials 34 (2022): e2201470. (e) R. Lan, Q. Wang, C. Shen, et al., “Humidity-Induced Simultaneous Visible and Fluorescence Photonic Patterns Enabled by Integration of Covalent Bonds and Ionic Crosslinks,” Advanced Functional Materials 31 (2021): 2106419.

[6] (a) L. Chen, S. Y. Yin, M. Pan, et al., “A Naked Eye Colorimetric Sensor for Alcohol Vapor Discrimination and Amplified Spontaneous Emission (ASE) From a Highly Fluorescent Excited-State Intramolecular Proton Transfer (ESIPT) Molecule,” Journal of Materials Chemistry C 4 (2016): 6962-6966. (b) Z. H. Zhu, Z. Ni, H. H. Zou, G. Feng, and B. Z. Tang, “Smart Metal–Organic Frameworks With Reversible Luminescence/Magnetic Switch Behavior for HCl Vapor Detection,” Advanced Functional Materials 31 (2021): 2106925. (c) X. Y. Dong, H. L. Huang, J. Y. Wang, H. Y. Li, and S. Q. Zang, “A Flexible Fluorescent SCC-MOF for Switchable Molecule Identification and Temperature Display,” Chemistry of Materials 30 (2018): 2160-2167. (d) W. J. Zhang, W. T. Chen, C. H. Li, et al., “Luminescence Detection of CH₂C<l₂ by Varying Cu…Cu Interactions in a Flexible Porous Coordination Polymer,” Inorganic Chemistry Frontiers 10 (2023): 6909-6917.

[7] J. I. Partanen, L. J. Partanen, and K. P. Vahteristo, “Traceable Thermodynamic Quantities for Dilute Aqueous Sodium Chloride Solutions at Temperatures From (0 to 80)°C. Part 1. Activity Coefficient, Osmotic Coefficient, and the Quantities Associated With the Partial Molar Enthalpy,” Journal of Chemical and Engineering Data 62 (2017): 2617-2632.

[8] (a) L. Gao, G. V. Baryshnikov, A. Ali, et al., “Hydrophilic Cocrystals With Water Switched Luminescence,” Angewandte Chemie International Edition 63 (2024): e202318497. (b) B. Lin, Q. Wang, Z. Qi, H. Xu, and D.-H. Qu, “Cucurbit[8]Uril-Mediated Multi-Color Fluorescence System for Time-Dependent Information Encryption,” Science China Chemistry 66 (2023): 1111-1119. (c) Y. Chen, A. Li, X. Li, et al., “Multi-Stimuli-Responsive Amphiphilic Pyridinium Salt and Its Application in the Visualization of Level 3 Details in Latent Fingerprints,” Advanced Materials 35 (2023): 2211917.

[9] (a) L. Chen, J. W. Ye, H. P. Wang, et al., “Ultrafast Water Sensing and Thermal Imaging by a Metal-Organic Framework With Switchable Luminescence,” Nature Communications 8 (2017): 15985. (b) Y. Jiang, Y. Cheng, S. Liu, et al., “Solid-State Intramolecular Motions in Continuous Fibers Driven by Ambient Humidity for Fluorescent Sensors,” National Science Review 8 (2021): nwaa135. (c) S. Mishra and A. K. Singh, “Optical Sensors for Water and Humidity and Their Further Applications,” Coordination Chemistry Reviews 445 (2021): 214063.

[10] (a) H. Kim, S. Yang, S. R. Rao, et al., “Water Harvesting From Air With Metal-Organic Frameworks Powered by Natural Sunlight,” Science 356 (2017): 430-434. (b) N. Hanikel, M. S. Prévot, and O. M. Yaghi, “MOF Water Harvesters,” Nature Nanotechnology 15 (2020): 348-355. (c) X. L. Lv, S. Yuan, L. H. Xie, et al., “Ligand Rigidification for Enhancing the Stability of Metal–Organic Frameworks,” Journal of the American Chemical Society 141 (2019): 10283-10293. (d) H. Lu, W. Shi, Y. Guo, W. Guan, C. Lei, and G. Yu, “Materials Engineering for Atmospheric Water Harvesting: Progress and Perspectives,” Advanced Materials 34 (2022): e2110079. (e) L. Shi, K. O. Kirlikovali, Z. Chen, and O. K. Farha, “Metal-Organic Frameworks for Water Vapor Adsorption,” Chemistry 10 (2024): 484-503.

[11] (a) Z. Zhang, Y. Ye, S. Xiang, and B. Chen, “Exploring Multifunctional Hydrogen-Bonded Organic Framework Materials,” Accounts of Chemical Research 55 (2022): 3752-3766. (b) X. Song, Y. Wang, C. Wang, et al., “Design Rules of Hydrogen-Bonded Organic Frameworks With High Chemical and Thermal Stabilities,” Journal of the American Chemical Society 144 (2022): 10663-10687. (c) Q. Yin, P. Zhao, R.-J. Sa, et al., “An Ultra-Robust and Crystalline Redeemable Hydrogen-Bonded Organic Framework for Synergistic Chemo-Photodynamic Therapy,” Angewandte Chemie International Edition 57 (2018): 7691.

[12] (a) Q. Huang, X. Chen, W. Li, et al., “Local Dynamics in a Hydrogen-Bonded Organic Framework for Adaptive Guest Accommodation With Programmable Luminescence,” Chemistry 9 (2023): 1241-1254. (b) B. Wang, R. B. Lin, Z. Zhang, S. Xiang, and B. Chen, “Hydrogen-Bonded Organic Frameworks as a Tunable Platform for Functional Materials,” Journal of the American Chemical Society 142 (2020): 14399-14416. (c) Z. Xiong, S. Xiang, Y. Lv, B. Chen, and Z. Zhang, “Hydrogen-Bonded Organic Frameworks as an Appealing Platform for Luminescent Sensing,” Advanced Functional Materials 34 (2024): 2403635. (d) B. Mohan, G. Singh, R. K. Gupta, et al., “Hydrogen-Bonded Organic Frameworks (HOFs): Multifunctional Material on Analytical Monitoring,” TrAc Trends in Analytical Chemistry 170 (2024): 117436.

[13] (a) M. Liang, S. Hu, Y. Han, et al., “A Multistimuli Responsive, Flexible Luminescent Framework and Its Applicability in Anticounterfeiting,” ACS Applied Materials & Interfaces 15 (2023): 37855-37866. (b) W. Wei, L. He, G. Han, et al., “Stimulus-Responsive Hydrogen-Bonded Organic Frameworks: Construction Strategies, Research Progress and Applications,” Coordination Chemistry Reviews 507 (2024): 215760. (c) Y.-H. Luo, X.-T. He, D.-L. Hong, et al., “A Dynamic 3D Hydrogen-Bonded Organic Frameworks With Highly Water Affinity,” Advanced Functional Materials 28 (2018): 1804822.

[14] (a) W. Q. Zhou, J. W. Ye, W. J. Zhang, M. J. Huang, L. Chen, and X. M. Chen, “Fluorescent Probes With Variable Intramolecular Charge Transfer: Constructing Closed-Circle Plots for Distinguishing D₂O From H₂O,” Analytical Chemistry 95 (2023): 8239-8249. (b) L. Yang, Y. Wang, E. Cui, et al., “Solvatochromic Covalent Organic Frameworks for the Low-Level Determination of Trace Water in Organic Solvents,” Sensors and Actuators B: Chemical 378 (2023): 133134.

[15] Y. Cheng, J. Wang, Z. Qiu, et al., “Multiscale Humidity Visualization by Environmentally Sensitive Fluorescent Molecular Rotors,” Advanced Materials 29 (2017): 1703900.

[16] (a) A. Yamamoto, T. Hamada, I. Hisaki, M. Miyata, and N. Tohnai, “Dynamically Deformable Cube-Like Hydrogen-Bonding Networks in Water-Responsive Diamondoid Porous Organic Salts,” Angewandte Chemie International Edition 52 (2013): 1709-1712. (b) L. S. Zhan, Y. Tang, W. M. Ning, et al., “Humidity Visualization Through a Simple Thermally Activated Delayed Fluorescent Emitter: The Role of Hydrogen Bonding,” Chemical Engineering Journal 454 (2023): 140182.

[17] (a) L. Sun, Y. Wang, F. Yang, X. Zhang, and W. Hu, “Cocrystal Engineering: A Collaborative Strategy Toward Functional Materials,” Advanced Materials 31 (2019): 1902328. (b) M. Li, Y. Liu, L. Shao, et al., “Pillararene-Based Variable Stoichiometry Co-Crystallization: A Versatile Approach to Diversified Solid-State Superstructures,” Journal of the American Chemical Society 145 (2023): 667-675. (c) L. Sun, W. Zhu, W. Wang, et al., “Intermolecular Charge-Transfer Interactions Facilitate Two-Photon Absorption in Styrylpyridine–Tetracyanobenzene Cocrystals,” Angewandte Chemie International Edition 56 (2017): 7831-7835. (d) H. Lin, X. Chang, D. Yan, W.-H. Fang, and G. Cui, “Tuning Excited-State-Intramolecular-Proton-Transfer (ESIPT) Process and Emission by Cocrystal Formation: A Combined Experimental and Theoretical Study,” Chemical Science 8 (2017): 2086-2090.

[18] (a) Y. Liu, Q. Zeng, B. Zou, Y. Liu, B. Xu, and W. Tian, “Piezochromic Luminescence of Donor-Acceptor Cocrystals: Distinct Responses to Anisotropic Grinding and Isotropic Compression,” Angewandte Chemie International Edition 57 (2018): 15670-15674. (b) T. Hashimoto, R. Oketani, M. Nobuoka, S. Seki, and I. Hisaki, “Single Crystalline, Non-Stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks,” Angewandte Chemie International Edition 62 (2023): e202215836. (c) Y. Wang, H. Wu, P. Li, et al., “Two-Photon Excited Deep-Red and Near-Infrared Emissive Organic Co-Crystals,” Nature Communications 11 (2020): 4633.

[19] J. K. Tang, L. H. Shao, J. Liu, et al., “Hydrogen-Bonded Organic Framework-Stabilized Charge Transfer Cocrystals for NIR-II Photothermal Cancer Therapy,” Journal of Materials Chemistry B 11 (2023): 8649-8656.

[20] X. Y. Gao, Y. Wang, E. Wu, et al., “Multivariate Hydrogen-Bonded Organic Frameworks With Tunable Permanent Porosities for Capture of a Mustard Gas Simulant,” Angewandte Chemie International Edition 62 (2023): e202312393.

[21] Q. Chen, T. Zhang, X. Chen, et al., “Tunable Fluorescence in Two-Component Hydrogen-Bonded Organic Frameworks Based on Energy Transfer,” ACS Applied Materials & Interfaces 14 (2022): 24509-24517.

[22] X. Y. Chen, L. H. Cao, Y. Yang, et al., “Water-Induced Single-Crystal to Single-Crystal Transformation of Ionic Hydrogen-Bonded Organic Frameworks With Enhanced Proton Conductivity,” Chemistry - A European Journal 29 (2023): e202300028.

[23] S. Park, J. E. Kwon, S. Y. Park, et al., “Crystallization-Induced Emission Enhancement and Amplified Spontaneous Emission From a CF3-Containing Excited-State Intramolecular-Proton-Transfer Molecule,” Advanced Optical Materials 5 (2017): 1700353.

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2024 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.