Robust Nanoporous Supramolecular Network through Charge

Subscriber access provided by University of Sunderland

Applications of Polymer, Composite, and Coating Materials

Robust Nanoporous Supramolecular Network through Charge-Transfer Interaction Xiao-Dong Yang, Ming Chen, Rui Zhu, Jie Zhang, and Banglin Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b14316 • Publication Date (Web): 06 Nov 2018 Downloaded from http://pubs.acs.org on November 10, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Robust Nanoporous Supramolecular Network through ChargeTransfer Interaction Xiao-Dong Yang†, Ming Chen†, Rui Zhu†, Jie Zhang†,* and Banglin Chen‡,* †MOE

Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, P. R. China ‡ Department of Chemistry, University of Texas at San Antonio, one UTSA Circle, San Antonio, Texas 78249-0698, USA ABSTRACT: A robust nanoporous supramolecular network stabilized by charge-transfer interactions has been successfully constructed based on the bipyridinium and the bicarboxylic acid with electron-donating hydroxyl pendant group, which exhibits high durability towards extensive acid/base condition (pH: 2-12), organic solvents and the plucking of metal ions. Furthermore, the separation capacity toward Rhodamine B and other dyes with the same charge and smaller molecular sizes has been realized in it. KEYWORDS: porous supramolecular network, charge transfer, bipyridinium, acid/basic durability, dye adsorption 1. Introduction Recently, the synthesis and property investigation of porous framework materials have become one of the hottest research topics in the field of materials chemistry.1-5 Among these, porous supramolecular networks (PSNs) mainly composed of discrete metal-organic or organic (also called SOFs, abbreviation of supramolecular organic frameworks) molecules have been advanced as new chemistry materials.6-8 Differing from other traditional porous framework materials such as metal–organic frameworks (MOFs), zeolite– imidazolate frameworks (ZIFs) and covalent organic frameworks (COFs) which are fabricated by molecular selfassembly via covalent or coordinate bonds, the discrete building modules in PSNs or SOFs are extended though supramolecular interactions.9-10 In comparison, supramolecular interactions own a larger range of strengths, directionality and reversibility which can guarantee effective modification over the structures and properties of the target PSNs or SOFs and further capacitate them with diverse functions.11-12 As a result, PSNs or SOFs possess some particular advantages such as solution processability and characterization, straightforward regeneration, easy purification, etc. For the majority of the existing PSNs such as some well-reported SOFs (SOF-7, PFC-1, TTBI, etc), their architectures are mainly organized by hydrogen bonds or π-π stacking interactions.13-15 Nevertheless, hydrogen bonds can be easily broken in basic environment and indeed PSNs or SOFs with high basic durability are still rarely reported to date. In addition, π-π stacking interactions are usually formed discretionarily between two aromatic rings just with appropriate packing orientation, the poorer controllability poses a huge barrier for the predictive design of target PSNs. These urgently addressed problems generate a demand for a new type of PSNs. Charge-transfer (CT) interactions as a specific type of noncovalent interactions have been widely studied in the field of supramolecular chemistry. Different from other kinds of supramolecular interactions, CT interactions are usually formed between electron-deficient (acceptor; such as bipyridinium, aromatic diimide, etc) and electron-rich (donor;

Scheme 1. Schematic representation of the synthesis strategy of CT-bearing PSNs based on bipyridinium molecule.

such as pyrenyl, dioxyarenes, tetrathiafulvalene, etc) moieties with highly directional nature.16-18 The inherent complementary character between donor and acceptor and the mixing of ground state with an excited charge-separated state endow CT interactions with a relative stronger strength.17 Furthermore, CT interactions have a larger formation tendency which can take place even when the involved donors and acceptors in extremely low concentration such as 1 μM.18 These traits highlight CT interactions from other supramolecular interactions. Thus, incorporating CT interactions into the framework of PSNs as the main connecting force can be a promising approach to improve current situation. Bipyridinium derivatives are well known for their electrondeficient nature and usually conduct CT interactions with electron-rich units ranging from inorganic ions to organic moieties due to their low-energy LUMO.19-20 These unique characters make them as the excellent candidates to fabricate PSNs with improved properties. Recognizing the enormous potential of this approach, our group has embarked on a program aimed at constructing CT-bearing PSNs with

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

bipyridinium molecules (Scheme 1). Herein, we report an unprecedented CT-bearing PSN called [Cd(Bpybc)(HIPA)(H2O)]·5H2O (PSN-Cd; H2BpybcCl2 = 1,1-bis(4carboxybenzyl)-4,4´-bipyridinium dichloride; H2HIPA = 5hydroxyisophthalic acid). The present compound possesses regular hexagon-shaped 1D channels in nanoscale extending along the c-axis and renders the first example of MOF-74 analogues fabricated by supramolecular interactions. Attractively, due to the strong CT interactions within the framework, PSN-Cd can exist steadily not only in pH = 2-12 aqueous solutions, organic solvents but also even without the assistance of metal ions, which is rarely reported in previous literatures. Especially, the dangling deprotonated benzyl acid moiety of Bpybc ligand and the uncovered hydroxy group of HIPA2- anion on the pore wall in PSN-Cd facilitates the formation of host–guest interactions with Rhodamine B to a large extent, thus realizing the rarely reported separation capacity toward Rhodamine B and other dyes with the same charge and smaller molecular sizes. 2. Results and discussion 2.1 Crystal structure Single-crystal X-ray diffraction analysis reveals that PSNCd crystallizes in the rhombohedral space group of R3 with a 3D honeycomb-shaped framework. Its asymmetric unit contains one crystallographically independent Cd(II) ion, one Bpybc ligand, one HIPA2− anion, one coordinated and five highly disordered guest water solvates (Figure S1). The central Cd(II) ion is coordinated in a distorted pentagonal bipyramidal fashion by seven oxygen atoms. Six of these oxygen atoms (O1, O2, O5, O6, O8#1 and O9#1; #1: -x+y+1/3, -x+2/3, z-1/3) are from the carboxylate groups of the organic ligands (Bpybc, HIPA2−) while the rest one (O1W) comes from the coordinated water molecule (Figure S2). Each HIPA2− anion bridges two Cd(II) ions to generate 1D left- or right-hand 31 helical chains (Figure S3) and the Bpybc ligands acting as lateral arms distribute around these helical chains (Figure 1a & S4). The effective pore aperture radius of these helical chains is 5.30 Å (Figure S5). Interestingly, neighboring helical chains are

Figure 1. (a) The left-handed helical chains with lateral Bpybc ligands in PSN-Cd. (b) The stacking mode of adjacent helical chains in PSN-Cd. (c) The view of honeycomb-shaped 3D framework in PSN-Cd. (d) The hexagon-shaped 1D pore in PSN-Cd.

Figure 2. The solid UV-Vis diffuse reflectance spectra of PSN-Cd, H2BpybcCl2 and H2HIPA. Insert: the photographs of PSN-Cd single crystal (a), H2BpybcCl2 (b) and H2HIPA (c).

linked with each other by CT interactions which occur among the electron-deficient pyridinium ring and electron-rich bicarboxylic HIPA2− anions containing electron-donating hydroxyl pedant group with centroid···centroid distances of 3.47 and 3.59 Å, interplanar angles of 2.11 and 2.13° (Figure 1b & S6a). These CT interactions can be further confirmed by the extra added characteristic band at 450 nm compared with H2BpybcCl2 and H2HIPA in the UV-vis reflection spectrum of PSN-Cd and also show up in its darker color (Figure 2).21-22 Additionally, the relatively weaker π–π stacking interaction between the benzene rings of Bpybc ligands in adjacent helical chains (3.73 Å, 0°) and the hydrogen bonds [O7 (H7)···O4, d = 2.62 Å] between every two adjacently separated helical chains with the same chirality also make some contributions (Figure S6b & S7 & Table S1). A 3D framework with honeycomb motif along the c axis can be found in PSN-Cd which is extended by CT interactions with the assistance of π– π stacking and hydrogen bond (Figure 1c). The pore diameter of these hexagonal channels is 20.30 Å with taking into account the van der Waals radius (Figure 1d). The void volume calculated by PLATON program is 43.7% (9160. 0 Å3 of 20982.4 Å3) without consideration of the guest molecules. Due to equal amounts of right- and left-handed helical chains, PSN-Cd exhibits no chirality as a whole structure. Notably, the packing structure of whole framework in PSN-Cd is identical to that recently described for MOF-74.23 However, in previous literatures, the frameworks of MOF-74 and its analogues are mainly extended via coordination bond.23-26 Thus PSN-Cd renders the first example of MOF-74 analogues which extends its 3D framework with supramolecular interactions. 2.2 Thermal and chemical stability studies In order to evaluate the thermal and chemical stability of PSN-Cd, we have conducted several meticulous studies. The variable-temperature powder X-ray diffraction (PXRD) data show that PSN-Cd can keep crystalline state at 120 C and begin to become amorphous above 130 C (Figure 3a). Furthermore, the PXRD patterns of PSN-Cd still remain unchanged after soaking in the aqueous solutions with pH = 212 (24 h) and some organic solvents (24 h) (Figure 3b & 3c), implying its excellent chemical stability which is even comparable to the well-known quite stable UiO series MOF


Page 2 of 7

Page 3 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 4. The interaction energy of CT interaction (a, b), π–π stacking (c), hydrogen bond (d). Figure 3. (a) Variable-temperature PXRD patterns for PSN-Cd measured from 30 °C to 180 °C. (b) PXRD patterns of PSN-Cd after soaking in aqueous solutions with pH value of 2-12 for 24 h. (c) PXRD patterns of PSN-Cd after soaking in some organic solvents for 24 h. (d) Energy-dispersive X-ray (EDX) spectroscopy of PSN-Cd before (red) and after (black) soaking in EDTA2- solution for 24 h. Inset: schematic representation of plucking Cd(II) ions from the framework of PSN-Cd.

materials.27 More interestingly, the main framework of PSNCd is still maintained even after the Cd(II) ions were plucked out by soaking the fresh samples in 0.1 mol/L EDTA2- solution for more than 24 h due to the complexation effect (Figure 3d & S8-S9). These data indicate that the supramolecular interactions in PSN-Cd can provide a powerful force to keep the integrity of the framework. To further elucidate which supramolecular interaction plays a key role for its high stability, DFT calculations were performed (Section 2 in Supporting Information). As shown in Figure 4, the binding energy of CT interactions is -41.87 kcal/mol and -39.00 kcal/mol, respectively, which even match some of coordination bonds (e.g. As-O: -43.38 -44.81 kcal/mol, Eu-O: -16.44 -79.87 kcal/mol, Ca-O: -6.18 -30.04 kcal/mol),28-30 while the binding energy of π–π stacking and hydrogen bond is just -17.84 kcal/mol and -18.65 kcal/mol, demonstrating a vital role of CT interaction for its structural stability. In the previous literatures, the frameworks of PSN materials are mainly connected by hydrogen bond or π–π stacking.13-15 Although some PSNs with high thermal stability, acid and solvent durability have been successfully synthesized, the example with high basic durability has never been reported because hydrogen bond can be easily broken in basic environment. By contrast, in PSN-Cd, CT interactions function as the main connecting force of the whole framework. So even though basic solution can perturb the intrinsic equilibrium state of the existing hydrogen bonds, it does not constitute destruction to the whole framework. 2.3 Vapor/gas/dye adsorption studies As a type of zwitterionic molecule, Bpybc owns a chargeseparated skeleton and is thought to be highly polarized. Thus the Bpybc-modified hexagonal channels in PSN-Cd may form stronger adsorbate–adsorbent interaction with larger polar guest molecules due to the electric field gradient produced by

its well-separated intramolecular charges in the framework.31 Along this line, vapor adsorption measurements were performed firstly. The activated sample of PSN-Cd was prepared by evacuation at 70 °C for 2 h and its weight changing curve reveals that all water molecules in the open channels have been completely removed (Figure S10). Meanwhile, the peaks of the PXRD pattern of the activated sample are essentially identical to the original one, confirming that the open channels are still remained in the absence of guest water molecules (Figure S11). The profiles of adsorption and desorption for PSN-Cd at room temperature (298 K) exhibit selective capabilities towards different guest molecules such as water 8.69 mmol/g (156.55 mg/g), methanol 5.31 mmol/g (170.14 mg/g), ethanol 3.59 mmol/g (165.39 mg/g) and cyclohexane 0.01 mmol/g (0.84 mg/g), which perfectly match their intrinsic polarities (molecule polarity: water > methanol > ethanol > cyclohexane) (Figure 5a). In addition, for other non-polar molecules with smaller sizes such as CO2 and N2, the dehydrated framework also does not show any appreciable uptakes (Figure S12 & S13). Notably, PSN-Cd can separate Rhodamine B (RB) from some common dyes with different charges and molecular sizes such as Coumarin 153 (C153), Sudan I (SI), Methyl violet (MV), Methylene blue (MLB), Methyl orange (MO) (Figure S14). Dye-uptake analyses were executed by soaking the freshly prepared crystals of PSN-Cd in CH3CN solutions containing the dyes mentioned above and their concentrations were monitored by UV-vis spectroscopy as a function of time. As shown in the inset of Figure 5b, the pink solution of RB fades to colorless within 48 h after the addition of PSN-Cd. Meanwhile the main absorption band of RB drops notably along with time and its concentration decreases to 3.6% after 48 h (Figure 5b & 5c). The concentration of the original RB solution also dramatically decreases when encountering PSNCd in the dark environment (Figure S15), which can exclude the possibility of photodegradation. The characteristic peak at 1705 cm-1 of –COOH group can be observed in the infrared spectra of the RB-loaded sample and its framework still remains unchanged as verified by PXRD pattern (Figure S16 & S17). Additionally, no pink color reappears when placing the RB-loaded sample into the pure CH3CN (Figure S18). Thus, this decontamination phenomenon of RB is reasonably attributed to the adsorption behaviour into the open channels of PSN-Cd rather than photodegradation or surface adsorption.



Figure 5. (a) The sorption isotherms of PSN-Cd toward different vapors at 298 K. Hollow symbols denote the adsorption branch, while the solid ones for the desorption branch. (b) Sequential UV-Vis spectra of RB in CH3CN solution (1×10-5 mol/L, 4 mL) in the presence of PSN-Cd (20 mg) with time. (c) The relevant dye contents in the CH3CN solutions after soaking PSN-Cd for 48 h. (d) Kinetic data fitting of RB adsorption over PSN-Cd using the pseudo-second-order kinetics model. (e) Selective adsorption capability of MV (2.5 × 10-6 mol/L, 2 mL) + RB (1 × 10-5 mol/L, 2 mL) in the presence of PSN-Cd (20 mg) with time. (f) Selective adsorption capability of MLB (5×10-6 mol/L, 2 mL) + RB (1×10-5 mol/L, 2 mL) in the presence of PSN-Cd (20 mg) with time.

Since the adsorption rate is a relatively crucial parameter to evaluate the efficiency of an adsorbent, the adsorption kinetics of PSN-Cd towards RB was measured. As shown in Figure 5d, the second-order kinetic constant (k2) is 5.87×10-2 g·min/mg (R2= 0.9838).32-33 The adsorption capacity of PSN-Cd toward RB calculated from the Langmuir equation is 14.8 mg/g (Figure S19).32-33 More interestingly, the RB solution with lower concentration (1×10-6 mol/L) can also be adsorbed by PSN-Cd verifying its strong adsorptive power towards RB (Figure S20). By contrast, other dyes exhibit no obvious adsorption phenomena throughout the whole testing process (Figure 5c & S21-S25). In order to further validate the selective separation performance of PSN-Cd, competition experiments were performed. The fresh sample of PSN-Cd was immersed into the mixed solutions of RB & C153, RB & SI, RB & MV, RB & MLB and RB & MO, respectively. The UV/vis spectra show that only RB can be effectively adsorbed, while the characteristic absorption bands of C153, SI, MV, MLB and MO exhibit no obvious changes (Figure 5e-5f & S26-S28). In addition, the color of the mixed solution almost changed to the pure C153, SI, MV, MLB and MO solution after about 48 h (the inserts of Figure 5e-5f & S26-S28). These distinctive results further suggest that only RB can be adsorbed by PSNCd although all of their molecular sizes are accessible. In

addition, the unchanged PXRD patterns of PSN-Cd after soaking in the CH3CN solutions of C153, SI, MV, BLM and MO can eliminate effect of the framework collapsing (Figure S29). Then questions arise: why can merely RB be adsorbed by PSN-Cd, and what is the driving force? As is well known, the selective adsorption of porous framework materials are almost based on the host–guest interactions or the ionexchange process.34-39 Due to its neutral framework, the selective adsorption behaviour of PSN-Cd is reasonably attributed to the host–guest interactions. In PSN-Cd, the pore walls of these open channels are decorated with the deprotonated carboxylate group (O3-C26-O4) of Bpybc ligand and the hydroxy group (-O7H7) of HIPA2- anion. The dangling carboxylate and uncovered hydroxy oxygen atoms can form hydrogen bond interactions with the carboxylate group of RB molecule which may act as a driving force for its selective adsorption (Figure S30). However, because of the hydrogen bond [O7 (H7)···O4, d = 2.53 Å] within the framework, no extra interaction can be generated between the H atom of hydroxy group and the F atom of C153 and N atom of MV, MLB, MO. As for SI molecule, the intramolecular hydrogen bond has prevented it to interact with the framework of PSN-Cd (Figure S31). Although many porous framework materials with RB adsorption capacity have been synthesized up to now, selective separation between RB and MV or MLB is rarely founded. This is because the adsorption process of RB reported previously is mainly on account of the ionexchange,40-43 so dyes with the same charge and smaller molecular size cannot be separated effectively from RB. By comparison, the current work provides a rather convenient routine to separate RB and MV or MLB. 3. Conclusions In summary, a neoteric PSN material with nano-sized honeycomb-like motif featuring as the MOF-74 analog has been successfully obtained based on bipyridinium ligand. Due to the strong CT interactions, the framework of the current compound can be maintained after soaking in pH = 2-12 aqueous solutions, organic solvents or even plucking out metal ions. Notably, the specific arrangement of the functional group on the pore wall makes it as the excellent candidate to separate dyes with the same charge. We believe that this work can not only provoke more studies to synthesize PSN or SOF materials with higher stability but also enrich the research field of dye purification, and further work is ongoing.

ASSOCIATED CONTENT Supporting Information is available free of charge on the ACS Publications website. Additional data (PDF) Crystallographic data for PSN-Cd (CIF)

AUTHOR INFORMATION Corresponding Author [email protected] [email protected]

ORCID Jie Zhang: 0000-0002-6195-8525 Banglin Chen: 0000-0001-8707-8115 Notes The authors declare no competing financial interest.


Page 4 of 7

Page 5 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ACKNOWLEDGMENT This work was supported by the grants from the National Natural Science Foundation of China (21573016/21871027, J.Z.), and partly supported by Welch Foundation (AX-1730, B.C.) and National Science Foundation (DMR-1606826, B.C.). REFERENCES (1) Waller, P. J.; AlFaraj, Y. S.; Diercks, C. S.; Jarenwattananon, N. N.; Yaghi, O. M. Conversion of Imine to Oxazole and Thiazole Linkages in Covalent Organic Frameworks. J. Am. Chem. Soc. 2018, 140, 9099-9103. (2) Jin, J.; Zhao, X.; Feng, P.; Bu, X. A Cooperative Pillar– Template Strategy as a Generalized Synthetic Method for Flexible Homochiral Porous Frameworks. Angew. Chem. Int. Ed. 2018, 57, 3737-3741. (3) Islamoglu, T.; Goswami, S.; Li, Z.; Howarth, A. J.; Farha, O. K.; Hupp, J. T. Postsynthetic Tuning of Metal– Organic Frameworks for Targeted Applications. Acc. Chem. Res. 2017, 50, 805-813. (4) Park, J.; Feng, D.; Yuan, S.; Zhou, H.-C. Photochromic Metal–Organic Frameworks: Reversible Control of Singlet Oxygen Generation. Angew. Chem. Int. Ed. 2015, 54, 430-435. (5) Dalrymple, S. A.; Shimizu, G. K. H. Crystal Engineering of a Permanently Porous Network Sustained Exclusively by Charge-Assisted Hydrogen Bonds. J. Am. Chem. Soc. 2007, 129, 12114-12116. (6) Bao, Z.; Xie, D.; Chang, G.; Wu, H.; Li, L.; Zhou, W.; Wang, H.; Zhang, Z.; Xing, H.; Yang, Q.; Zaworotko, M. J.; Ren, Q. L.; Chen, B. Fine Tuning and Specific Binding Sites with a Porous Hydrogen-Bonded Metal-Complex Framework for Gas Selective Separations. J. Am. Chem. Soc. 2018, 140, 4596-4603. (7) Hasell, T.; Chong, S. Y.; Jelfs, K. E.; Adams, D. J.; Cooper, A. I. Porous Organic Cage Nanocrystals by Solution Mixing. J. Am. Chem. Soc. 2012, 134, 588-598. (8) Yang, W.; Greenaway, A.; Lin, X.; Matsuda, R.; Blake, A. J.; Wilson, C.; Lewis, W.; Hubberstey, P.; Kitagawa, S.; Champness, N. R.; Schröder, M. Exceptional Thermal Stability in a Supramolecular Organic Framework: Porosity and Gas Storage. J. Am. Chem. Soc. 2010, 132, 14457-14469. (9) Nugent, P. S.; Rhodus, V. L.; Pham, T.; Forrest, K.; Wojtas, L.; Space, B.; Zaworotko, M. J. A Robust Molecular Porous Material with High CO2 Uptake and Selectivity. J. Am. Chem. Soc. 2013, 135, 10950-10953. (10) Hasell, T.; Wu, X.; Jones, J. T. A.; Bacsa, J.; Steiner, A.; Mitra, T.; Trewin, A.; Adams, D. J.; Cooper, A. I. Triply Interlocked Covalent Organic Cages. Nature chem. 2010, 2, 750-755. (11) Klivansky, L. M.; Hanifi, D.; Koshkakaryan, G.; Holycross, D. R.; Gorski, E. K.; Wu, Q.; Chai, M.; Liu, Y. A Complementary Disk-Shaped π Electron Donor–Acceptor Pair with High Binding Affinity. Chem. Sci. 2012, 3, 2009-2014. (12) Fustin, C.-A.; Guillet, P. Metallo-Supramolecular Block Copolymers. Adv. Mater. 2007, 19, 1665-1673. (13) Yin, Q.; Zhao, P.; Sa, R.-J.; Chen, G.-C.; Lu, J.; Liu, T.-F.; Cao, R. An Ultra-Robust and Crystalline Redeemable Hydrogen-Bonded Organic Framework for Synergistic Chemo-Photodynamic Therapy. Angew. Chem. Int. Ed. 2018, 57, 7691-7696. (14) Lu, J.; Perez-Krap, C.; Suyetin, M.; Alsmail, N. H.; Yan, Y.; Yang, S.; Lewis, W.; Bichoutskaia, E.; Tang, C. C.;

Blake, A. J.; Cao, R.; Schröder, M. A Robust Binary Supramolecular Organic Framework (SOF) with High CO2 Adsorption and Selectivity. J. Am. Chem. Soc. 2014, 136, 12828-12831. (15) Mastalerz, M.; Oppel, I, M. Rational Construction of an Extrinsic Porous Molecular Crystal with an Extraordinary High Specific Surface Area. Angew. Chem. Int. Ed. 2012, 51, 5252-5255. (16) Das, A; Ghosh, S. Supramolecular Assemblies by Charge-Transfer Interactions between Donor and Acceptor Chromophores. Angew. Chem. Int. Ed. 2014, 53, 2038-2054. (17) Hunter, C. A.; Lawson, K. R.; Perkins, J.; Urch, C. J. Aromatic Interactions. J. Chem. Soc., Perkin Trans. 2001, 2, 651-669. (18) Kumar, N. S. S.; Gujrati, M. D.; Wilson, J. N. Evidence of Preferential π-stacking: A Study of Intermolecular and Intramolecular Charge Transfer Complexes. Chem. Commun. 2010, 46, 5464-5466. (19) Yang, X.-D.; Zhu, R.; Sun, L.; Guo, R.-Y.; Zhang, J. Phototriggered Mechanical Movement in A Bipyridiniumbased Coordination Polymer Powered by Electron Transfer. Inorg. Chem. 2018, 57, 2724-2729. (20) Shi, W.; Xing, F.; Bai, Y.-L.; Hu, M.; Zhao, Y.; Li, M.X.; Zhu, S. High Sensitivity Viologen for a Facile and Versatile Sensor of Base and Solvent Polarity in Solution and Solid State in Air Atmosphere. ACS Appl. Mater. Interfaces 2015, 7, 14493-14500. (21) Shimomura, S.; Matsuda, R.; Tsujino, T.; Kawamura, T.; Kitagawa, S. TCNQ Dianion-Based Coordination Polymer Whose Open Framework Shows Charge-Transfer Type Guest Inclusion. J. Am. Chem. Soc. 2006, 128, 16416-16417. (22) Ohmori, O.; Kawano, M.; Fujita, M. Crystal-to-Crystal Guest Exchange of Large Organic Molecules within a 3D Coordination Network. J. Am. Chem. Soc. 2004, 126, 1629216293. (23) Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B.; O´Keeffe, M; Yaghi, O. M. Rod Packings and Metal−Organic Frameworks Constructed from Rod-Shaped Secondary Building Units. J. Am. Chem. Soc. 2005, 127, 1504-1518. (24) Deng, H.; Grunder, S.; Cordova, K. E.; Valente, C.; Furukawa, H.; Hmadeh, M.; Gandara, F.; Whalley, A. C.; Liu, Z.; Asahina, S.; Kazumori, H.; O´Keeffe, M.; Terasaki, O.; Stoddart, J. F.; Yaghi, O. M. Large-Pore Apertures in a Series of Metal-Organic Frameworks. Science 2012, 336, 1018-1023. (25) Zhou, W.; Wu, H.; Yildirim, T. Enhanced H2 Adsorption in Isostructural Metal−Organic Frameworks with Open Metal Sites: Strong Dependence of the Binding Strength on Metal Ions. J. Am. Chem. Soc. 2008, 130, 15268-15269. (26) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores. J. Am. Chem. Soc. 2008, 130, 10870-10871. (27) Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye, U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P. Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chem. Mater. 2010, 22, 6632-6640. (28) Tian, C.; Zhao, J.; Ou, X.; Wan, J.; Cai, Y.; Lin, Z.; Xing, B. Enhanced Adsorption of p-Arsanilic Acid from Water by Amine-Modified UiO-67 as Examined Using Extended X-ray Absorption Fine Structure, X-ray Photoelectron Spectroscopy, and Density Functional Theory. Environ. Sci. Technol. 2018, 52, 3466-3475.



(29) Li, L.; Wang, W.; Zhu, Y.; Zhang, W.; Xu, H.; Zhou, L.; Liu, X. Bond Energy, Preferential Occupancy and Spontaneous Reduction Ability of Eu3+ Doped in CaAl2Si2O8. J. Alloys Compd. 2018, 731, 496-503. (30) Adamescu, A.; Hamilton, I. P. and Al-Abadleh, H. A. Density Functional Theory Calculations on the Complexation of p-Arsanilic Acid with Hydrated Iron Oxide Clusters: Structures, Reaction Energies, and Transition States. J. Phys. Chem. A 2014, 118, 5667-5679. (31) Sun, J.-K.; Ji, M.; Chen, C.; Wang, W.-G.; Wang, P.; Chen, R.-P.; Zhang, J. A Charge-polarized Porous Metal– Organic Framework for Gas Chromatographic Separation of Alcohols from Water. Chem. Commun. 2013, 49, 1624-1626. (32) Li, Q.; Xue, D.-X.; Zhang, Y.-F.; Zhang, Z.-H.; Gao, Z.; Bai, J. A Dual-Functional Indium–Organic Framework towards Organic Pollutant Decontamination via Physically Selective Adsorption and Chemical Photodegradation. J. Mater. Chem. A 2017, 5, 14182-14189. (33) Haque, E.; Jun, J. W.; Jhung, S. H. Adsorptive Removal of Methyl Orange and Methylene Blue from Aqueous Solution with a Metal-Organic Framework Material, Iron Terephthalate (MOF-235). J. Hazard. Mater. 2011, 185, 507-511. (34) Liu, Y.; Cui, Y.; Zhang, C.; Du, J.; Wang, S.; Bai, Y.; Liang, Z.; Song, X. Post-Cationic Modification of a Pyrimidine-Based Conjugated Microporous Polymer for Enhancing the Removal Performance of Anionic Dyes in Water. Chem. Eur. J. 2018, 24, 7480-7488. (35) Fan, H.; Gu, J.; Meng, H.; Knebel, A.; Care, J. HighFlux Membranes Based on the Covalent Organic Framework COF-LZU1 for Selective Dye Separation by Nanofiltration. Angew. Chem. Int. Ed. 2018, 57, 4083-4087. (36) Oveisi, M.; Asli, M. A.; Mahnoodi, N. M. MIL-Ti Metal-Organic Frameworks (MOFs) Nanomaterials as Superior Adsorbents: Synthesis and Ultrasound-Aided Dye Adsorption from Multicomponent Wastewater Systems. J. Hazard. Mater. 2018, 347, 123-140. (37) Zhao, X.; Mao, C.; Luong, K. T.; Lin, Q.; Zhai, Q.-G.; Feng, P.; Bu, X. Framework Cationization by Preemptive Coordination of Open Metal Sites for Anion-Exchange Encapsulation of Nucleotides and Coenzymes. Angew. Chem. Int. Ed. 2016, 55, 2768-2772. (38) Gibson, L. T. Mesosilica Materials and Organic Pollutant Adsorption: Part B Removal from Aqueous Solution Chem. Soc. Rev. 2014, 43, 5173-5182. (39) Han, Y.; Sheng, S.; Yang, F.; Xie, Y.; Zhao, M.; Li, J.R. Size-Exclusive and Coordination-Induced Selective Dye Adsorption in a Nanotubular Metal–Organic Framework. J. Mater. Chem. A 2015, 3, 12804-12809. (39) Sun, C.-Y.; Wang, X.-L.; Qin, C.; Jin, J.-L.; Su, Z.-M.; Huang, P.; Shao, K.-Z. Solvatochromic Behavior of Chiral Mesoporous Metal–Organic Frameworks and Their Applications for Sensing Small Molecules and Separating Cationic Dyes. Chem. Eur. J. 2013, 19, 3639-3645. (40) Xing, S.; Bing, Q.; Song, L.; Li, G.; Liu, J.; Shi, Z.; Feng, S.; Xu, R. The Uncommon Channel-Based Ln-MOFs for Highly Selective Fe3+ Detection and Superior Rhodamine B Adsorption. Chem. Eur. J. 2016, 22, 16230-16235. (41) Meng, Q.; Xin, X.; Zhang, L.; Dai, F.; Wang, R. Sun, D. A Multifunctional Eu MOF as a Fluorescent pH Sensor and Exhibiting Highly Solvent-Dependent Adsorption and Degradation of Rhodamine B. J. Mater. Chem. A 2015, 3, 24016-24021.

(42) Yi, F.-Y.; Li, L.-P.; Wu, D.; Su, Z.-M. A Series of Multifunctional Metal–Organic Frameworks Showing Excellent Luminescent Sensing, Sensitization, and Adsorbent Abilities. Chem. Eur. J. 2015, 21, 11475-11482. (43) He, Y.-C.; Yang, J.; Kan, W.-Q.; Ma, J.-F. An Ideal Metal–Organic Rhombic Dodecahedron for Highly Efficient Adsorption of Dyes in an Aqueous Solution. CrystEngComm 2013, 15, 848-851.


Page 6 of 7

Page 7 of 7 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


SYNOPSIS TOC


7

Robust Nanoporous Supramolecular Network through Charge

Recommend Documents