A semi-rigid molecular clip-based molecular crystal gearshift - ACS

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A semi-rigid molecular clip-based molecular crystal gearshift Jia-Rui Wu, Bao Li, Jiangwei Zhang, and Ying-Wei Yang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b20108 • Publication Date (Web): 07 Dec 2018 Downloaded from http://pubs.acs.org on December 7, 2018

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ACS Applied Materials & Interfaces

A Semi-Rigid Molecular Clip-Based Molecular Crystal Gearshift Jia-Rui Wu,† Bao Li,‡ Jiang-Wei Zhang,§ and Ying-Wei Yang†,* †State

Key Laboratory of Inorganic Synthesis and Preparative Chemistry, International Joint

Research Laboratory of Nano-Micro Architecture Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China,

‡

State Key Laboratory of

Supramolecular Structure and Materials, Institute of Theoretical Chemistry, Jilin University, Changchun 130012, P. R. China, §State Key Laboratory of Catalysis & Gold Catalysis Research Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China. KEYWORDS: molecular clip, crystalline materials, X-ray diffraction, host-guest chemistry, molecular crystal gearshift

ABSTRACT: A new version of molecular clip, with semi-rigid symmetrical crab-type architecture and flexible cavity size, has been successfully designed and synthesized via a one-pot Friedel-Crafts alkylation reaction. The X-ray single crystal diffraction data provide a simple and intuitive explanation, not only for its well preorganized and regulated conformation but also for the selective and tunable guest binding capability. For the first time, the newly designed molecular clip was demonstrated to be not only a controllable variable-speed nonporous adsorption material

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in solution iodine capture, but also capable of on-off switching in volatile iodine capture. The presented new concept of molecular crystal gearshift directly from the molecular clip crystals represents an important advance in the development of synthetic receptor chemistry, which will exert a significant influence on small molecule crystallography.

Supramolecular toolbox containing multiple types of synthetic receptors with tailored structures and excellent host-guest properties contribute significantly to different areas of research including host-guest chemistry, gas storage and adsorption, targeted drug delivery, molecular machinery, and energy materials. Therefore, the design and synthesis of supramolecular synthetic receptors with tunable binding affinities and responsive properties has been one of the cutting-edge research topics along with the rapid development of supramolecular chemistry.1-26 Among them, molecular tweezers and clips, a wide class of acyclic-type molecular receptors with cavities of flexible size are most persuasive examples.18-26 Accordingly, their syntheses, binding properties, supramolecular functions and stimuli-responsiveness have been intensively studied.19-21,24 However, there are still some key issues of the aforementioned acyclic receptor systems remained to be solved or enhanced. For example, in the syntheses of molecular tweezers and clips derivatives, repetitive Diels-Alder reactions followed by further oxidization with 2,3-dichloro-5,6-dicyano1,4-benzoquinone (DDQ) are usually needed,20 limiting their wide use and further development. Besides tedious synthetic steps, over-flexible and unregulated/uncontrollable belt-shaped conformations also limited their cavity adaptability and application.17 Enlightened by the synthetic chemistry of certain macrocyclic ligands, such as cucurbit[n]urils and pillar[n]arenes that possess stable pumpkin- or pillar-shaped cavity architecture with good rigidity by connecting their monomers with methylene bridges,3,8 we come up with an idea of designing a methylene-bridged

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open-shell molecular clip with regulated conformations of certain rigidity via a facile and concise synthetic approach. Here, we report a wholly original form of methylene-bridged, self-rigid molecular clip (MC) system, namely 1,4-bis(2,4,6-trimethoxybenzyl)naphthalene, (Figure 1a), which has three features: (i) two pincers of 1,3,5-trimethoxybenzene are covalently connected to a naphthalene by methylene bridges at the 1- and 4’-substitution positions, (ii) two sidewalls form an extended cavity, endowing its guest-binding capability, (iii) the naphthalene backbone together with the switching units of methylene linkers guaranty its tunable binding affinity and responsive property. Benefiting from these structural characteristics, they are expected, and also have been found, to have extraordinary conformation-variable structures, selective guest binding capability, and more importantly, efficient application as a molecular crystal gearshift.

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Figure 1 (a) Synthetic route to MC and X-ray single-crystal structures of (b) MCα, (c) DCM⊂MC, (d) 2(H2O)⊂MC, (e) I2⊂2(MC), (f) mX⊂MC, and (g) MCβ. The dihedral angle changes from 44.42° to 58.20°, representing the simi-rigidity of the MC skeleton. The synthetic strategy for MC is highly efficient and extremely straightforward, where a facile one-pot Lewis acid-catalyzed method was employed. Briefly, 1,4-bis(chloromethyl)naphthalene was reacted with an excess amount of 1,3,5-trimethoxybenzene as catalyzed by AlCl3 in a FriedelCrafts alkylation reaction, leading to the formation of MC host in a good yield of 70% (Scheme S1, Figures S1-S3). Significantly, a series of high-quality single crystals of MC and its host-guest complexes with different targets, referred to as MCα, I2⊂2(MC), 2(H2O)⊂MC, DCM⊂MC and mX⊂MC, (mX represents m-xylene, Figure 1b-1g, Tables S1-S2, Figures S7-S13) have been

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obtained. To our surprise, inorganic and organic targets (iodine, water, dichloromethane, and mxylene) with different shapes, sizes, and stoichiometries, can be stably hosted in MC, and multiple intermolecular interactions enhance these sandwich type of host-guest complexes (C-H···π distance 2.851 Å, O- H···O distance 2.494 Å, Cl···π distance 3.590 Å, I···π distance, 3.123 Å), which demonstrated that the MC is highly effective for cargo capture owing to the expanded πelectron rich cavity. The MC receptor is not of an absolute rigid structure, and the dihedral angle values of the two pincers rendered a sharp increase in the order of MCα (44.42°) < DCM⊂MC (49.76°) < 2(H2O)⊂MC (51.66°) < I2⊂2(MC) (54.15°) < mX⊂MC (57.15°), giving an approximate 13 degree angle change due to the well-known size-fit effect and guest induced fit theory in host-guest chemistry. In addition, the diameter of the incircle of MCα is about 7.4 Å (Figure 1b, the number of 7.4 Å was obtained by subtracting two van der Waals radius of oxygen atoms from the distance between two farthest methoxy groups). Furthermore, molecular configuration with two pincers inverted and distorted also simultaneously obtained (referred to as MCβ, Figure 1g), which reflects the conformational diversity and controllability of MC molecular crystals in the solid state. Single crystal structure analysis on MCα and MCβ reveals a dense packing in both crystalline phases, as stabilized by multiple C-H···O and π···π interactions (Figures S7-S8, C-H···O distance for MCα, 2.745 Å; C-H···O distance for MCβ, 2.677 Å, 3.263 Å; π···π distance for MCα, 3.581 Å; π···π distance for MCβ, 3.607 Å). But, an average torsion angle of 20° between the 1,3,5trimethoxybenzene units and the naphthalene ring and a stretching of two 1,3,5-trimethoxybenzene units in an opposite direction were found in MCβ (Figure S8b), in sharp contrast to the 3° angle and same direction stretching in MCα (Figure S7b). This means, in the phase transition from MCα to MCβ, one of the claws needs a rotation of ca. 180 degree, followed by stretching two pincers at

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a certain angle in the opposite direction along with the plane of naphthalene ring, suggesting that the symmetric and extended π-electron cavity is completely destroyed and the high-density πelectron atmosphere no longer exists in MCβ crystal solid. Radionuclide fission products, such as the hazardous iodine isotope (129I and

131I),

which are

uncontrollable spilled out and severely damage on human health during nuclear waste treatment or nuclear accidents, e.g., the Fukushima nuclear disaster.27-29 According to the single crystal structure of I2⊂2(MC) as mentioned above, each iodine molecule is located in the extended cavity between two opposite but malposed MC molecules (Figure S11c), and typical charge-transfer (donor-acceptor) interactions (I···π distance, 3.123 Å) enhance the stability of the host-guest complexes. So, we anticipate that this MC receptor can serve as a new material for iodine uptake. On top of that, combined with the multiformity and controllability of MC molecular crystals, we introduce a concept of “molecular crystal gearshift” for the first time.

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Figure 2. (a) Photographs showing the color changes with different speeds when crystalline solids (DCM⊂MC, MCα, and MCβ, 5mg respectively) were placed in an iodine/n-hexane solution (0.02 mmol/L). (b) Efficiency of iodine removal from n-hexane solution by MCα (blue), DCM⊂MC (black), MCβ (red), and MCIα (purple). (c) the color changes of the crystalline solids (MCα, MCβ, DCM⊂MC, and MCIα) upon exposure to iodine vapor. To be more confirmative, MCα, MCβ and DCM⊂MC crystals were immersed in a I2/n-hexane solution (0.02 mol/L), respectively. Time-dependent photographs and UV-Vis experiments were taken to compare the adsorption rates, both quantitatively and qualitatively (Figures 2a-b,S18). As was expected, the reddish brown solution gradually changed to colorless with different speeds (Figure 2c). For MCα, iodine concentration decreased to 0.003 mol/L after 140 min of successive adsorption (Figure S18c). With regard to MCβ, its adsorption rate is far less than the former, and

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a 400 min continuous solution adsorption can achieve the same effect as the 140 min of MCα (Figure S18b). Interestingly, host-guest complex crystals of DCM⊂MC, without further desolvation or activation, possess the highest adsorption capacity and efficiency of all systems. UV-vis experiment confirmed that iodine removal efficiency was more than 90% after only 50 min solid-solution contact time (Figure S18a).

Scheme 1. Interconversion of the crystals of various MC-based single-crystal structures in solution and the solid states. (a) DCM⊂MC was obtained by recrystallization of MC in CH2Cl2. (b) I2⊂2(MC), with iodine stably hosted in the cavity of MC, was obtained by cocrystallization of MC and iodine in toluene. (c) MCα, possessing an effective extended cavity, was obtained by recrystallization from toluene. (d) MCβ, without any effective extended cavity, was obtained by recrystallization from chlorocyclohexane, which can also be obtained by heating the crystals of MCα, DCM⊂MC, or I2⊂2(MC).

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Based on the results of iodine adsorption in solution, we can easily find that the adsorption rates render a decrease in the order of DCM⊂MC> MCα> MCβ, confirming a three-speed gear shift adsorption system regulated by MC. The fastest adsorption rate of DCM⊂MC indicates that the host-guest complexes of I2⊂2(MC) are more stable than DCM⊂MC. Thus, straightforward guestexchange upon exposure to iodine solution resulted in the transition from DCM⊂MC to I2⊂2(MC), and the PXRD patterns before and after the adsorption procedures are all in consistency with the simulated patterns (Figure S19), further proving that the crystalline phase transition induced by guest exchange really occurred. CH2Cl2 molecules not only occupy the ringent cavities but also “protect" them, thus improving the available active cavity volume and reducing the interference from multiple intermolecular interactions due to all kinds of packing modes to a certain extent. As to MCβ crystal, the PXRD pattern after complete capture of iodine in solution is consistent with the simulated pattern from I2⊂2(MC), also in step with the pattern of MCα crystals after in-solution iodine loading (Fig. S21-S22), indicating that all the two structures changed to I2⊂2(MC) upon capture of iodine in solution. However, for MCβ crystal, it is necessary initially to trigger the configuration conversion, and recover its π-electron cavities as well as binding capability, which gives a good explanation for its inefficiency and poor performance in solution iodine adsorption. For further explanation, an important MC isomer (MCIα) by linking the 1,3,5trimethoxybenzene at the 1’- and 5’- substitution positions (Scheme S2 and Fig. S4-S6) has been designed and successfully synthesized. From the crystal structural analysis, the two claws are in parallel (3.569 Å) and in a reversed direction in the MCIα crystal (Figure S13), and no effective π-electron donor cavity exists in a single molecule, thus unsurprisingly, scarcely any iodine was

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adsorbed (Figure 2b,S18d), which gives a strong evidence for the necessity of extended cavity of MC hosts in iodine capture. All in all, the available π-electron cavity volume indeed determines the nature of this binding speed diversity.

Figure 3. Schematic representation of the variable speed iodine adsorption cycle process, i.e., the new concept of molecular crystal gearshift constructed by MC. Three-speed direct-shift effect of MC crystals in solution iodine binding kindled our interest, whether some transformation relationship between these “gearshifts” exist. Evidently, a similar crystal to crystal transition from MCα/DCM⊂MC to MCβ was observed during heating (Scheme 1), and the PXRD profiles of these two transformed crystals are all in good agreement with the patterns simulated from MCβ (Figure S23-S26). In other words, these crystal phase transformations are also equivalent to a shift from high speed gear to low speed gear. Meanwhile, I2⊂2(MC) crystals laden with guests can also be transformed to MCβ upon heating, as verified by PXRD and DSC analysis (Figure S29-30), which means the low speed gear is the thermodynamically favored phase, and can also be regarded as the loop start and loop end for this variable speed adsorption cyclic process. As shown in Scheme 1 and Figure 3, the speed changing

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adsorption system based on MC can be shifted down by continuous heating, and geared up by easy recrystallization in toluene (restore medium speed) or CH2Cl2 (restore high speed), proving to be a fully stimuli-responsive/controllable new system. The newfangled variable speed control of MC crystals in solution iodine binding inspired us to further investigate these properties in air. Thereupon, MCα, MCβ, DCM⊂MC, and MCIα were placed under I2 vapor atmosphere for several hours to investigate their I2 vapor sorption capacity. As depicted in Figures 2c and S32, MCα and DCM⊂MC crystals gradually changed from colorless to distinctive brown. But, thermogravimetric (TG) measurements give a clearly description that only MCα crystals present an effective adsorption (Figure. S33-S37), for which the saturation adsorption value (176 mg/g) in line with the 1:2 crystal structure of I2⊂2(MC). Furthermore, the PXRD patterns indicate that I2 was brought into the host framework, and a singlecrystal-to-single-crystal transformation successively generated an iodine-loaded system (Figure S38), suggesting that the adsorption of iodine on this tweezer system are predominantly of receptor-substrate binding process. Moreover, hardly any weight loss below 150 °C indicates a relatively high thermal stability of iodine in MCα crystals (Figure S34). But, to our surprise, MCβ solids barely adsorb iodine in the air, even after a longer adsorption time (Figure 2c and S32c), which means iodine vapor cannot, or at any rate cannot easily induce the conformational conversion and regain the binding capability, just as liable to occur in solution iodine adsorption. However, as to DCM⊂MC, CH2Cl2 cannot stably exist, and a solid–solid–transition from DCM⊂MC to MCβ occurred due to the relatively high temperature of experimental process (Figure S25-26), which gives a good explanation for the poor adsorption in the air (Figure S32b,S36).

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Interestingly, the iodine vapor adsorption capability of MC is completely on-off controllable. The molecular conformation of MCα represents the “turn-on” state, which possesses the loading/capture ability toward iodine no matter in the form of vapor or in a solution. However, the MCβ crystalline phase without π-electron cavities represents the “turn-off” configuration, barely adsorbing volatile iodine. Finally, N2 adsorption experiments revealed that MCα and MCβ crystalline solids are all nonporous (Figure S44-45), giving a much more convincing evidence that MCβ crystals are in a completely “closed” state in iodine vapor atmosphere. CONCLUSION In conclusion, we presented a new type of dynamic molecular clip, with tidy synthetic ease, and multiple and absolutely controllable conformations. Taking advantage of this unique structural feature, inorganic or organic species different in shape, number and size, can be stably hosted, including but not limited to dichloromethane, water, m-xylene and iodine, which makes molecular clip possess a wide array of potential applications in the capture of volatile radionuclide fission products, purification of BTEX chemicals, and water harvesting.27,30,31 Furthermore, the included angle changes of molecular clips also provide a simple and intuitive explanation for guest-induced fit theory and cavity adaptability in host-guest chemistry and crystal engineering, further confirming the importance of this rigid/steerable backbone in molecular recognition and cargo storage.32-35 What’s more, we have demonstrated that this molecular clip could construct a variable speed cyclic adsorption system for iodine solution uptake, where facile switching among the high, middle and low speed gear (adsorption rate) was achieved as a result of the crystalline-phase/ molecular-configuration controllable manual control. Importantly, our results led to a new concept of molecular crystal gearshift where such an organic small molecule can parade as an adsorbent in pollutant disposal with specified range of operating rates. However, there must be more potential 12


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gearshifts yet to be found or tested, and hopefully our current work based on this newly synthesized molecular clip will help to inspire and enable further discoveries and industry applications of new molecular crystalline materials. ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: Chemical synthesis and characterization, crystal structure analysis, thermogravimetric analysis, crystallographic data for MCα (CIF/1852634), crystallographic data for DCM⊂MC (CIF/ 1852632), crystallographic data for 2(H2O)⊂MC (CIF/1852631), crystallographic data for I2⊂2(MC) (CIF/1852635, 1852629), crystallographic data for mX⊂MC (CIF/1852633), crystallographic data for MCβ (CIF/1852590), Crystallographic data for MCIα (CIF/1852636), and all experimental details (PDF). AUTHOR INFORMATION Corresponding Author Prof. Ying-Wei Yang E-mail: [email protected]; [email protected] Funding Sources National Natural Science Foundation of China (21871108, 51673084); Jilin Province-University Cooperative Construction Project – Special Funds for New Materials (SXGJSF2017-3); Fundamental Research Funds for the Central Universities; JLU Cultivation Fund for the National Science Fund for Distinguished Young Scholars for financial support.

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A semi-rigid molecular clip-based molecular crystal gearshift - ACS

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