Mechanistic insights of evaporation-induced actuation in supramolecular crystals

Piotrowska, Roxana; Hesketh, Travis; Wang, Haozhen; Martin, Alan R. G.; Bowering, Deborah; Zhang, Chunqiu; Hu, Chunhua T.; McPhee, Scott A.; Wang, Tong; Park, Yaewon; Singla, Pulkit; McGlone, Thomas; Florence, Alastair J.; Tuttle, Tell; Ulijn, Rein V.; Chen, Xi

doi:10.1038/s41563-020-0799-0

Cited by 57 publications

(67 citation statements)

References 38 publications

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“…The nqp-4w–to–nqp-2w process is energy consuming with an entropy gain. The uphill energy of 158 kcal mol −1 is remarkably larger than the energy variations involved in the guest-induced structural transformations of typical FMOFs 9 , 15 , 18 – 20 , 62 . Once nqp-2w-L/R form, the structures are converted to lcp-2w because the latter is 47 kcal mol −1 more stable than nqp-2w-L/R.…”

Section: Discussionmentioning

confidence: 91%

A spin-crossover framework endowed with pore-adjustable behavior by slow structural dynamics

Zhao

Liu

et al. 2022

Nat Commun

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Host-guest interactions play critical roles in achieving switchable structures and functionalities in porous materials, but design and control remain challenging. Here, we report a two-dimensional porous magnetic compound, [FeII(prentrz)2PdII(CN)4] (prentrz = (1E,2E)−3-phenyl-N-(4H-1,2,4-triazol-4-yl)prop-2-en-1-imine), which exhibits an atypical pore transformation that directly entangles with a spin state transition in response to water adsorption. In this material, the adsorption-induced, non-uniform pedal motion of the axial prentrz ligands and the crumpling/unfolding of the layer structure actuate a reversible narrow quasi-discrete pore (nqp) to large channel-type pore (lcp) change that leads to a pore rearrangement associated with simultaneous pore opening and closing. The unusual pore transformation results in programmable adsorption in which the lcp structure type must be achieved first by the long-time exposure of the nqp structure type in a steam-saturated atmosphere to accomplish the gate-opening adsorption. The structural transformation is accompanied by a variation in the spin-crossover (SCO) property of FeII, i.e., two-step SCO with a large plateau for the lcp phase and two-step SCO with no plateau for the nqp phase. The unusual adsorption-induced pore rearrangement and the related SCO property offer a way to design and control the pore structure and physical properties of dynamic frameworks.

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Section: Discussionmentioning

confidence: 91%

A spin-crossover framework endowed with pore-adjustable behavior by slow structural dynamics

Zhao

Liu

et al. 2022

Nat Commun

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“…Such high viscosity shares similarities with our recently observed evaporation‐induced H‐bonding strengthening of water confined in WR tripeptide crystals. [ 43 ] Note that the high viscosity of PG's nanoconfined water does not contradict the fast WR speed and high power density, which could be explained by PG's small size and large surface‐to‐volume ratio that facilitate water diffusion. Thermodynamically, materials’ WR actuation is driven by the chemical potential difference between water inside the material and water vapor outside.…”

Section: Resultsmentioning

confidence: 99%

High Energy and Power Density Peptidoglycan Muscles through Super‐Viscous Nanoconfined Water

et al. 2022

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Water-responsive (WR) materials that reversibly deform in response to humidity changes show great potential for developing muscle-like actuators for miniature and biomimetic robotics. Here, it is presented that Bacillus (B.) subtilis' peptidoglycan (PG) exhibits WR actuation energy and power densities reaching 72.6 MJ m −3 and 9.1 MW m −3 , respectively, orders of magnitude higher than those of frequently used actuators, such as piezoelectric actuators and dielectric elastomers. PG can deform as much as 27.2% within 110 ms, and its actuation pressure reaches ≈354.6 MPa. Surprisingly, PG exhibits an energy conversion efficiency of ≈66.8%, which can be attributed to its super-viscous nanoconfined water that efficiently translates the movement of water molecules to PG's mechanical deformation. Using PG, WR composites that can be integrated into a range of engineering structures are developed, including a robotic gripper and linear actuators, which illustrate the possibilities of using PG as building blocks for high-efficiency WR actuators. IntroductionDespite more than a century of research, mechanical actuators, which typically transduce electrical fields, [1] chemical energy, [2] heat, [3,4] and pressurized gas/liquid [5] into motions, still cannot

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“…Reports of reversible SCSC transformations associated with large volume and mass changes are rare in the literature (Supplementary Table 2 ). The 50% total volumetric shrinkage and 36% total weight loss observed for the present material, which are reminiscent of the expansion of clay structures by adding ethylene glycol 39 , 40 , are larger than those observed for other typical single-crystal materials that undergo reversible SCSC transformations, and they are even comparable to those of two recently discovered porous crystalline materials that contain biomolecules, i.e., ferritin and tripeptide, that demonstrate giant expandability in response to guest sorption 31 , 32 . Although detailed atomic level structural information is important for understanding these super-adaptive crystal lattices, such information is difficult to obtain for these biomolecules because of the disordered nature of the guests in their pores and the disruption of the single-crystal lattice that occurs upon giant expansion.…”

Section: Discussionmentioning

confidence: 42%

“…13 ) 41 , 42 . The strong hydrogen-bond interactions not only spatially define the motion of the sulfate dianions, they also play pivotal roles in fastening the crystal lattice during the giant structural transformation 22 , 31 , 32 . Therefore, the single-crystal structure is maintained after elimination of the chelating ligands.…”

Section: Discussionmentioning

confidence: 99%

“…However, the SCSC transformations in typical single-crystal materials are primarily small because of the rigid chemical bonds and spatial constraint in the crystal lattice. Recently, high-grade structural transformations involving large shifts in mass and volume have been observed in several porous single crystals as a consequence of guest sorption 31 – 33 . Such counterintuitive phenomena are usually associated with special interactions between the material’s constituent molecules.…”

Section: Introductionmentioning

confidence: 99%

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Giant single-crystal-to-single-crystal transformations associated with chiral interconversion induced by elimination of chelating ligands

Zhao

Xie

et al. 2021

Nat Commun

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Numerous single crystals that exhibit single-crystal-to-single-crystal (SCSC) transformations have been reported, and some of them show great promise for application to advanced adsorption materials, magnetic switches, and smart actuators. However, the development of single crystals with super-adaptive crystal lattices capable of huge and reversible structural change remains a great challenge. In this study, we report a ZnII complex that undergoes giant SCSC transformation induced by a two-step thermal elimination of ethylene glycol chelating ligands. Although the structural change is exceptionally large (50% volume shrinkage and 36% weight loss), the single-crystal nature of the complex persists because of the multiple strong hydrogen bonds between the constituent molecules. This allows the reversible zero-dimensional to one-dimension and further to three-dimensional structural changes to be fully characterized by single-crystal X-ray diffraction analyses. The elimination of chelating ligands induces a chiral interconversion in the molecules that manifests as a centric-chiral-polar symmetric variation of the single crystal. The study not only presents a unique material, featuring both a periodic crystal lattice and gel-like super-ductility, but also reveals a possible solid-state reaction method for preparing chiral compounds via the elimination of chelating ligands.

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Mechanistic insights of evaporation-induced actuation in supramolecular crystals

Cited by 57 publications

References 38 publications

A spin-crossover framework endowed with pore-adjustable behavior by slow structural dynamics

A spin-crossover framework endowed with pore-adjustable behavior by slow structural dynamics

High Energy and Power Density Peptidoglycan Muscles through Super‐Viscous Nanoconfined Water

Giant single-crystal-to-single-crystal transformations associated with chiral interconversion induced by elimination of chelating ligands

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