Solvents in crystalline materials typically exist either as structural components that stabilize the framework or as adsorbed guests that modulate properties, yet achieving their orthogonal coexistence within a single system remains challenging. This study proposes a natural mineral-inspired solvent hierarchy strategy that enables the concurrent achievement of framework stability and dynamic responsiveness in hydrogen-bonded organic frameworks (HOFs) through the orthogonal integration of structural and adsorbed solvents. We have validated the feasibility of this solvent hierarchy approach based on four model systems with progressively increasing stability and dynamism: (1) unstable HOFs containing only adsorbed solvents, (2) unstable HOFs with low-binding-energy structural solvents, (3) stable HOFs incorporating strong-fitted structural solvents, and (4) stable HOFs with structural solvents and dynamically adjustable adsorption solvents. Crystallographic and theoretical analyses reveal that the superior stability of structural solvents originates from the high-electron-density oxygen of the DMSO S═O bond, which acts as a strong hydrogen-bond acceptor, forming stable N─H···O═S bonds with amine groups. The host's aggregation-induced emission (AIE) characteristics allow real-time optical monitoring of reversible single-crystal-to-single-crystal transformations without compromising structural integrity, demonstrating promising applications for visual water content and water leakage detection. This work not only establishes a new paradigm in solvent engineering for developing smart crystalline materials but also expands the design possibilities for functional porous frameworks.
| [1] |
M. Ma, L. Guo, D. G. Anderson, and R. Langer, “Bio-Inspired Polymer Composite Actuator and Generator Driven by Water Gradients,” Science 339 (2013): 186–189.
|
| [2] |
H. Bi, Y. Shi, T. Wang, S. Deng, B. Z. Tang, and P. Wei, “Tandem Solid-Solution Phase Post-Synthetic Modification of Porous Molecular Crystals for In-Situ Generation of Fluorophores,” Angewandte Chemie International Edition 63 (2024): e202409211.
|
| [3] |
S. Fakhreddine and S. Fendorf, “The Effect of Porewater Ionic Composition on Arsenate Adsorption to Clay Minerals,” Science of the Total Environment 785 (2021): 147096.
|
| [4] |
H. Arazoe, D. Miyajima, K. Akaike, et al., “An Autonomous Actuator Driven by Fluctuations in Ambient Humidity,” Nature Materials 15 (2016): 1084–1089.
|
| [5] |
S. Dong, J. Leng, Y. Feng, et al., “Structural Water as an Essential Comonomer in Supramolecular Polymerization,” Science Advances 3 (2017): eaao0900.
|
| [6] |
J. L. Atwood, L. J. Barbour, A. Jerga, and B. L. Schottel, “Guest Transport in a Nonporous Organic Solid via Dynamic van der Waals Cooperativity,” Science 298 (2002): 1000–1002.
|
| [7] |
K. Jie, Y. Zhou, E. Li, and F. Huang, “Nonporous Adaptive Crystals of Pillararenes,” Accounts of Chemical Research 51 (2018): 2064–2072.
|
| [8] |
N. B. McKeown, “Nanoporous Molecular Crystals,” Journal of Materials Chemistry 20 (2010): 10588–10597.
|
| [9] |
A. Comotti, S. Bracco, A. Yamamoto, et al., “Engineering Switchable Rotors in Molecular Crystals With Open Porosity,” Journal of the American Chemical Society 136 (2014): 618–621.
|
| [10] |
V. A. Russell, C. C. Evans, W. Li, and M. D. Ward, “Nanoporous Molecular Sandwiches: Pillared Two-Dimensional Hydrogen-Bonded Networks With Adjustable Porosity,” Science 276 (1997): 575–579.
|
| [11] |
L. Zhang, L. Zheng, Y. Song, et al., “Molecular-Squeeze Triggers Guest Desorption From Sponge-Like Macrocycle Crystals,” Angewandte Chemie International Edition 64 (2025): e202420048.
|
| [12] |
Z. Wang, L. Zhao, Z. Zhang, et al., “Superhydrophobic and Self-Healing Porous Organic Macrocycle Crystals for Methane Purification Under Humid Conditions,” Journal of the American Chemical Society 147 (2025): 4210–4218.
|
| [13] |
J. Huang, H. Feng, L. Zhang, and K. Jie, “Forward- and Retro-Vapofluorochromism of Sponge-Like Macrocycle Crystals,” Angewandte Chemie International Edition 64 (2025): e202500022.
|
| [14] |
X.-H. Wu, P. Luo, Z. Wei, et al., “Guest-Triggered Aggregation-Induced Emission in Silver Chalcogenolate Cluster Metal–Organic Frameworks,” Advanced Science 6 (2019): 1801304.
|
| [15] |
B. Wang, R. He, L.-H. Xie, et al., “Microporous Hydrogen-Bonded Organic Framework for Highly Efficient Turn-Up Fluorescent Sensing of Aniline,” Journal of the American Chemical Society 142 (2020): 12478–12485.
|
| [16] |
P. Wei, X. He, Z. Zheng, et al., “Robust Supramolecular Nano-Tunnels Built From Molecular Bricks,” Angewandte Chemie International Edition 60 (2021): 7148–7154.
|
| [17] |
H. Zhao, S. Hu, M. Liang, and P. Xue, “Heterostructure of Hydrogen-Bonded Organic Frameworks for White Light Emission and Information Encryption,” Advanced Optical Materials 13 (2025): 2402321.
|
| [18] |
Z. Zhang, T. Lieu, C.-H. Wu, et al., “Solvation-Dependent Switching of Solid-State Luminescence of a Fluorinated Aromatic Tetrapyrazole,” Chemical Communications 55 (2019): 9387–9390.
|
| [19] |
A. Karmakar, R. Illathvalappil, B. Anothumakkool, et al., “Hydrogen-Bonded Organic Frameworks (HOFs): A New Class of Porous Crystalline Proton-Conducting Materials,” Angewandte Chemie International Edition 55 (2016): 10667–10671.
|
| [20] |
S. Yu, G.-L. Xing, L.-H. Chen, T. Ben, and B.-L. Su, “Crystalline Porous Organic Salts: From Micropore to Hierarchical Pores,” Advanced Materials 32 (2020): 2003270.
|
| [21] |
T. Takeda, M. Ozawa, and T. Akutagawa, “Jumping Crystal of a Hydrogen-Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System,” Angewandte Chemie International Edition 58 (2019): 10345–10352.
|
| [22] |
X. Jing, P. Ju, H. Xie, et al., “Linker-Regulated Imine-Based Covalent Organic Frameworks Enable Dual-Mode Fluorescence Emission as Stable Internal Reference Signal,” Aggregate 6 (2025): e70183.
|
| [23] |
N. C. Jeong, B. Samanta, C. Y. Lee, O. K. Farha, and J. T. Hupp, “Coordination-Chemistry Control of Proton Conductivity in the Iconic Metal–Organic Framework Material HKUST-1,” Journal of the American Chemical Society 134 (2012): 51–54.
|
| [24] |
J. Xiao, A. R. M. Shaheer, C. Liu, T.-F. Liu, and R. Cao, “Hydrogen-Bonded Organic Framework Core–Shell Composite for Synergistic Antimicrobial Therapy,” Aggregate 5 (2024): e481.
|
| [25] |
M. O'Shaughnessy, J. Glover, R. Hafizi, et al., “Porous Isoreticular Non-Metal Organic Frameworks,” Nature 630 (2024): 102–108.
|
| [26] |
B.-T. Liu, T. Li, S.-H. Gong, et al., “Air-Stable Radical Polycyclic Aromatic Hydrogen-Bonded Organic Frameworks,” Chem 11 (2025): 102445.
|
| [27] |
Z. Zhang, Y. Ye, S. Xiang, and B. Chen, “Exploring Multifunctional Hydrogen-Bonded Organic Framework Materials,” Accounts of Chemical Research 55 (2022): 3752–3766.
|
| [28] |
N. Malek, T. Maris, M. Simard, and J. D. Wuest, “Molecular Tectonics. Selective Exchange of Cations in Porous Anionic Hydrogen-Bonded Networks Built From Derivatives of Tetraphenylborate,” Journal of the American Chemical Society 127 (2005): 5910–5916.
|
| [29] |
H. Li, C. Chen, Q. Li, et al., “An Ultra-Stable Supramolecular Framework Based on Consecutive Side-by-Side Hydrogen Bonds for One-Step C2H4/C2H6 Separation,” Angewandte Chemie International Edition 63 (2024): e202401754.
|
| [30] |
Y. Yang, L. Li, R.-B. Lin, et al., “Ethylene/Ethane Separation in a Stable Hydrogen-Bonded Organic Framework Through a Gating Mechanism,” Nature Chemistry 13 (2021): 933–939.
|
| [31] |
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.
|
| [32] |
J. Lü, C. Perez-Krap, M. Suyetin, et al., “Robust Binary Supramolecular Organic Framework (SOF) With High CO2 Adsorption and Selectivity,” Journal of the American Chemical Society 136 (2014): 12828–12831.
|
| [33] |
Z.-J. Lin, S. A. R. Mahammed, T.-F. Liu, and R. Cao, “Multifunctional Porous Hydrogen-Bonded Organic Frameworks: Current Status and Future Perspectives,” ACS Central Science 8 (2022): 1589–1608.
|
| [34] |
I. Hisaki, S. Nakagawa, N. Ikenaka, et al., “A Series of Layered Assemblies of Hydrogen-Bonded, Hexagonal Networks of C3-Symmetric π-Conjugated Molecules: A Potential Motif of Porous Organic Materials,” Journal of the American Chemical Society 138 (2016): 6617–6628.
|
| [35] |
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.
|
| [36] |
J.-H. Zhang, Z. M. Ge, J. Wang, D.-C. Zhong, and T.-B. Lu, “Hydrogen-Bonded Organic Frameworks for Photocatalytic Synthesis of Hydrogen Peroxide,” Nature Communications 16 (2025): 2448.
|
| [37] |
P.-Q. Zhang, Q. Li, Z.-K. Wang, et al., “[5]Rotaxane, Linear Polymer and Supramolecular Organic Framework Constructed by Nor-Seco-Cucurbit[10]Uril-Based Ternary Complexation,” Chinese Chemical Letters 34 (2023): 107632.
|
| [38] |
I. Hisaki, H. Toda, H. Sato, N. Tohnai, and H. Sakurai, “A Hydrogen-Bonded Hexagonal Buckybowl Framework,” Angewandte Chemie International Edition 56 (2017): 15294–15298.
|
| [39] |
K. J. Msayib, D. Book, P. M. Budd, et al., “Nitrogen and Hydrogen Adsorption by an Organic Microporous Crystal,” Angewandte Chemie International Edition 48 (2009): 3273–3277.
|
| [40] |
R. Zhang, H. Daglar, C. Tang, et al., “Balancing Volumetric and Gravimetric Capacity for Hydrogen in Supramolecular Crystals,” Nature Chemistry 16 (2024): 1982–1988.
|
| [41] |
W. Xiao, C. Hu, and M. D. Ward, “Guest Exchange Through Single Crystal-Single Crystal Transformations in a Flexible Hydrogen-Bonded Framework,” Journal of the American Chemical Society 136 (2014): 14200–14206.
|
| [42] |
J. R. Holst, A. Trewin, and A. I. Cooper, “Porous Organic Molecules,” Nature Chemistry 2 (2010): 915–920.
|
| [43] |
X. He, H. Bi, and P. Wei, “Luminescent Organic Molecular Frameworks From Tetraphenylethylene-Based Building Blocks,” Journal of Materials Chemistry C 11 (2023): 3675–3691.
|
| [44] |
T.-H. Chen, I. Popov, W. Kaveevivitchai, et al., “Thermally Robust and Porous Noncovalent Organic Framework With High Affinity for Fluorocarbons and CFCs,” Nature Communications 5 (2014): 5131.
|
| [45] |
Q. Huang, W. Li, Z. Mao, et al., “An Exceptionally Flexible Hydrogen-Bonded Organic Framework With Large-Scale Void Regulation and Adaptive Guest Accommodation Abilities,” Nature Communications 10 (2019): 3074.
|
| [46] |
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.
|
| [47] |
W. Yang, A. Greenaway, X. Lin, et al., “Exceptional Thermal Stability in a Supramolecular Organic Framework: Porosity and Gas Storage,” Journal of the American Chemical Society 132 (2010): 14457–14469.
|
| [48] |
X. Jiang, X. Cui, A. J. E. Duncan, et al., “Topochemical Synthesis of Single-Crystalline Hydrogen-Bonded Cross-Linked Organic Frameworks and Their Guest-Induced Elastic Expansion,” Journal of the American Chemical Society 141 (2019): 10915–10923.
|
| [49] |
Q. Huang, W. Li, Z. Mao, et al., “Dynamic Molecular Weaving in a Two-Dimensional Hydrogen-Bonded Organic Framework,” Chem 7 (2021): 1321–1332.
|
| [50] |
T. Adachi and M. D. Ward, “Versatile and Resilient Hydrogen-Bonded Host Frameworks,” Accounts of Chemical Research 49 (2016): 2669–2679.
|
| [51] |
S. Sen, N. Hosono, J.-J. Zheng, et al., “Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene Over Ethane,” Journal of the American Chemical Society 139 (2017): 18313–18321.
|
| [52] |
H. Yamagishi, H. Sato, A. Hori, et al., “Self-Assembly of Lattices With High Structural Complexity From a Geometrically Simple Molecule,” Science 361 (2018): 1242–1246.
|
| [53] |
Y.-G. Huang, Y. W. Shiota, M.-Y. Su, et al., “Superior Thermoelasticity and Shape-Memory Nanopores in a Porous Supramolecular Organic Framework,” Nature Communications 7 (2016): 11564.
|
| [54] |
V. I. Nikolayenko, D. C. Castell, D. P. van Heerden, and L. J. Barbour, “Guest-Induced Structural Transformations in a Porous Halogen-Bonded Framework,” Angewandte Chemie International Edition 57 (2018): 12086–12091.
|
| [55] |
J. Wang, S. Yang, L. Zhang, et al., “Constructing Flexible Crystalline Porous Organic Salts via a Zwitterionic Strategy,” Journal of the American Chemical Society 146 (2024): 31042–31052.
|
| [56] |
Y. Wang, X. Hou, and C. Liu, “Combustible Ice Mimicking Behavior of Hydrogen-Bonded Organic Framework at Ambient Condition,” Nature Communications 11 (2020): 3124.
|
| [57] |
Y. Shi, S. Wang, W. Tao, et al., “Multiple yet Switchable Hydrogen-Bonded Organic Frameworks With White-Light Emission,” Nature Communications 13 (2022): 1882.
|
| [58] |
P. Brunet, M. Simard, and J. D. Wuest, “Molecular Tectonics. Porous Hydrogen-Bonded Networks With Unprecedented Structural Integrity,” Journal of the American Chemical Society 119 (1997): 2737–2738.
|
| [59] |
Y. Zhang, S. Xie, Z. Zeng, and B. Z. Tang, “Functional Scaffolds From AIE Building Blocks,” Matter 3 (2020): 1862–1892.
|
| [60] |
T. Wang, X. He, J. Xu, et al., “Adaptive and Dynamic Nonintertwined Assembly of Rigid and Flexible Rings,” CCS Chemistry 7 (2024): 105–115.
|
| [61] |
M. J. K. Horner, T. Holman, and M. D. Ward, “Architectural Diversity and Elastic Networks in Hydrogen-Bonded Host Frameworks: From Molecular Jaws to Cylinders,” Journal of the American Chemical Society 129 (2007): 14640–14660.
|
| [62] |
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 53 (2013): 1709–1712.
|
| [63] |
G. Pawley, “Unit-Cell Refinement From Powder Diffraction Scans,” Journal of Applied Crystallography 14 (1981): 357–361.
|
| [64] |
W.-Z. Sun, W.-J. Zhang, J.-T. Xu, et al., “Beyond Molecular Design: Cocrystallization in Hydrogen-Bonded Organic Frameworks for Energy-Conserving Dehydration and Real-Time Luminescent Humidity Detection,” Aggregate 6 (2025): e721.
|
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