Multiple Efficient Fluorescence Emission from Cucurbit[10]uril

Subscriber access provided by UNIVERSITY OF TOLEDO LIBRARIES

Article

Multiple Efficient Fluorescence Emission from Cucurbit[10]uril[CdCl ] -Based Pillared Diamond Porous Supramolecular Frameworks 4

16

8-

Yu-Qing Yao, Ying-Jie Zhang, Yun-Qian Zhang, Zhu Tao, Xin-Long Ni, and Gang Wei ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b15673 • Publication Date (Web): 01 Nov 2017 Downloaded from http://pubs.acs.org on November 2, 2017

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 free 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 accessible to all readers and 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.

ACS Applied Materials & Interfaces 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 8

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

Multiple Efficient Fluorescence Emission from Cucurbit[10]uril-[Cd4Cl16]8--Based Pillared Diamond Porous Supramolecular Frameworks Yu-Qing Yao,a Ying-Jie Zhang,b Yun-Qian Zhang,a Zhu Tao,a Xin-Long Ni,*a and Gang Wei*c a. The Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Department of Chemistry, Guizhou University, Guiyang 550025, China. b. Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232, Australia. c. CSIRO Manufacturing PO Box 218, Lindfield, NSW 2070, Australia. Keywords: cucurbit[10]uril, porous frameworks, solid fluorescent materials, outer surface interactions, white-light-emitting

ABSTRACT: Cucurbit[10]uril (Q[10] or CB[10]), with the largest rigidly cavity (ca. 1.0 nm) yet characterized in the cucurbiturils family, and indeed among all artificial macrocyclic receptors to date, has been successfully exploited to construct a novel Q[10][Cd4Cl16]8--based pillared diamond porous supramolecular framework. Single-crystal X-ray diffraction analysis revealed that the 3D open-nanotube-type porous framework is constructed from free Q[10] molecules and [Cd4Cl16]8- cluster anions through the outer surface interactions of Q[10]. Notably, the Q[10]-based porous framework host can accommodate guest dyes, such as rhodamine B (G1), pyrenemethanamine hydrochloride (G2), and bathocuproine hydrochloride (G3), to form solid materials with efficient redgreen-blue (RGB) fluorescence. This work not only exemplifies a facile approach for the construction of macrocycle-based porous frameworks, but also offers a simple, lower cost, yet still highly efficient means of preparing multi-emitting, including white-lightemitting, solid luminescent materials.

Porous materials, have attracted considerable interest in recent years because of their novel structures and potential broad applications in gas storage/separation,1-5 catalysis,6-8 drug delivery9,10 and energy-related fields.11-15 Among them, supramolecular macrocycle-derived frameworks (e.g. those based on calix[n]arene,16-18 cyclodextrin,19,20 cucurbit[n]uril,21-28 and pillar[n]arene29-31), which combine both intrinsic and extrinsic cavities in certain crystalline forms or amorphous states, offer new properties in porous functional materials. For example, Atwood demonstrated that the cavity of calix[4]arene in a solid assembly can take up and transport vinyl bromide molecules.16 Stoddart et.al. found that a γ-CD-MOF extended framework could be utilized to separate various alkylaromatic derivatives and chiral aromatic and alicyclic compounds.19,20 Huang and coworkers reported that pillar[6]arene-based crystalline or amorphous materials could selectively capture and separate styrene from mixtures. 29 From a structural viewpoint, the series of homologues cucurbit[n]urils (Q[n]s32,33 or CB[n]s34), which process rigid cavities and portals of sizes in the range 4.4~10.7 Å, and a common cavity depth of 9.1 Å,35-39 are eminently suitable molecular building blocks for macrocycle-based porous materials. In fact, several groups, such as those of Kim, 21,22 Kögerler,23 Tian, 24 Atwood,25 Cao,26 and ourselves,27 have independently developed and exploited a

series of discrete Q[n]-based porous frameworks with promising gas or guest adsorption and separation properties. However, a number of experimental results in this field have suggested that the prediction of the packing of such macrocyclic molecular assemblies remains a great challenge because the intermolecular forces maintaining such arrays are poorly interpreted and controlled. In 2014, based on our own research and that of other groups, we proposed that the outer-surface interactions of cucurbit[n]urils,40 that is, noncovalent interactions (e. g., hydrogen bonding, ion−dipole interactions, and so on) of their electrostatically positive outer surfaces, is the main driving force in the formation of various Q[n]-based supramolecular architectures and porous frameworks.41-46 In particular, this is the case for those constructed from Q[n]s and inorganic anions, such as polychloride d-transition metal anions [Md-blockClx]y– through the outer surface interactions of Q[n].47-50 In this type of supramolecular assembly, the polychloride d-transition metal anions play a linking role and connect Q[n] molecules through their outer surface interactions, enabling the assembly of porous frameworks in high yield. We therefore tentatively refer to them as Q[n]-based supramolecular inorganic anionorganic frameworks (SAOFs). This strategy has proved to be a useful and facile approach for preparing Q[n]-derived porous frameworks. Thus, Q[n]s, serve as ideal building

ACS Paragon Plus Environment


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

blocks, and can be used to construct not only the wellknown MOFs, SOFs and COFs, but also emerging SAOFs, which could become an active branch in macrocycle-based porous frameworks. Meanwhile, the preparation of highly fluorescent photofunctional materials by accommodating fluorophore guests in coordinating hosts and macrocyclic receptors has emerged as a highly promising strategy.51-60 However, somewhat surprisingly porous materials including macrocycle-based frameworks capable of displaying intense fluorescence have been scarcely been reported.61-64 This may be attributed to the following factors: (i) the porous frameworks effectively quench the emissions of the included guest, owing to heavy-atom effects of the transition metal hinges and/or host−guest charge-transfer interactions, (ii) a lack of guest-binding ability, and (iii) pore sizes is too small to accommodate larger fluorophore molecules. In view of the above, and drawing on our research experience in Q[n] chemistry, in the present work, we report a crystalline pillared diamond porous supramolecular framework (SAOF-1) constructed from Q[10]65,66 (the largest rigid cavity yet characterized in the Q[n] family and indeed among all synthesized artificial macrocyclic receptors, with portal diameters of 10.7–12.6 Å and a volume of ca. 870 Å3). The Q[10]-[Cd4Cl16]8–-based SAOF-1 has novel 3D open-nanotube-type pores and exhibits good adsorption of various fluorophore guests to fabricate multiple solid-state luminescent materials with efficient fluorescence emissions. Microcrystals of SAOF-1 could be obtained almost instantaneously in near-quantitative yield (>90%) simply by mixing solutions of Q[10] and CdCl2 in 8.0 M aqueous HCl (Video in the ESI). Titration 1H NMR spectra further confirmed this conclusion (Figure S1). Single crystals of suitable quality for X-ray determination could be obtained from the microcrystal precipitates within one week, but the crystals were small and data was collected on MX beam lines at the Australian Synchrotron facility (Figures S2). The PXRD pattern of the microcrystals was similar to the simulated pattern from the collected single-crystal data, suggesting that the obtained microcrystals and single crystals had the same structural features (Figures S3). Figure 1 shows the detailed crystal structure of SAOF-1, which is characterized by a 3D pillared diamond porous framework constructed of Q[10] molecules and poly chloride-cadmium cluster anions ([Cd4Cl16]8–) (Figure 1a). Figure 1b shows its topological structure, which can be viewed as a stacking of parallel hexahedral cages, each of which is constructed from six Q[10] molecules and twelve cluster anions (Figure 1c). Each surface of the parallel hexahedral cage is inserted into a Q[10] molecule, and each side of the parallel hexahedral cage is inserted into a [Cd4Cl16]8– anion. The cage has twelve sides with the same topological length (2.4 nm), according to the measured angles between two neighboring sides (55.9° or 124.1°), the six same topological surface area of each cage and the topological volume of each cage were calculated as 4.9 nm2 and 8.2 nm3, respectively. The TEM image of SAOF-1 also

Page 2 of 8

showed its porosity, it can be seen that every seven alternations of light and

Figure 1. Crystal structure of SAOF-1: (a) overall views of the supramolecular assembly constructed from Q[10] molecules and [Cd4Cll6]8- anions; (b) topological structure of SAOF-1 based on parallel stacked hexahedra; (c) details of each parallel hexahedron; (d) schematic representation of the 3D open-nanotube-type parallelepiped cage.

Figure 2. (a) Crystal stacking structure of SAOF-1; (b) TEM image of the microcrystals.

Figure 3. Detailed interactions between a Q[10] molecule and four [Cd4Cll6]8- anions: (a) top view, (b) side view; (c) detailed interaction between a [Cd4Cl6]8- anion and four Q[10] molecules. Hydrogen atoms and solvent water molecules are omitted for clarity.

dark correspond to about 20 nm, consistent with the crystal structure (Figure 2). Close inspection reveals that each


Page 3 of 8

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


Q[10] molecule interacts with four [Cd4Cl16]8− anions (Figure 3a and 3b) and, in turn, each [Cd4Cl16]8− anion interacts with four Q[10] molecules (Figure 3c) through the outer surface interactions, that is, the electrostatic interaction between the electropositive outer surface of Q[10]s and [Cd4Cl16]8− anions. Thus, we obtained a Q[10]based SAOF. Above, we have described the porous structure of the SAOF-1, which has 3D open-nanotube-type porosity with large open portals, that is, the portals of Q[10] molecules. Most importantly, as mentioned previously, the open portal size is up to 1.0 nm, and we anticipated that there would be sufficient space to accommodate large aromatic compounds, that the rigid hydrophobic cavities of Q[n]s can often yield high-quality and intense fluorescence emissions.55,67 To obtain such porous-based solid fluorescent materials, SOAF-1 had to meet at least two requirements: (1) selection of a suitable solvent in which the selected organic compounds or fluorophore guest are freely soluble, while SOAF-1 remains highly stable; (2) efficient absorption of the target organic compounds or fluorophore by SOAF-1. Considering the solubility of [Cd4Cl16]8− anions in SAOF-1, neutral water or alcohols are not suitable solvents, whereas SAOF-1 shows high stability in acetonitrile. However, some of the selected organic compounds or fluorophores show poor solubility in acetonitrile. After numerous attempts to select a solvent, we turned to use of mixed solvents of water or alcohols with acetonitrile. A typical mixed solvent (Vwater/Vacetonitrile=1/9) was eventually selected for all experiments in this work. The PXRD pattern of SAOF-1 soaked in this solvent for more than 24h was similar to that of fresh microcrystals collected by filtration from HCl solution (Figure S4), indicating that SAOF-1 was very stable in this medium. Next, three typical fluorophore guests, rhodamine B (G1), pyrenemethanamine hydrochloride (G2), and bathocuproine hydrochloride (G3) were selected from a range of well-known dyes due to their novel photophysical properties after adsorption in SAOF-1. Experimental results indicated that such SAOF-1-adsorptionbased luminescent materials exhibited excellent red-greenblue (RGB) fluorescence emissions in the solid state. They could therefore be used as three primary color materials in fabricating multi-emitting fluorescent materials. Rhodamine B (G1) is a well-known efficient redemitting fluorophore in solution, but gives a low quantum yield in the solid state due to aggregation-induced fluorescence quenching (ACQ). Loading the white solid SAOF-1 with G1 (G1@SAOF-1) gave a pink powder under daylight, which showed a red fluorescence emission with a maximum intensity peak at 608 nm (Figure 4d). Detailed adsorption experiments revealed rapid adsorption equilibrium when microcrystals of SAOF-1 were added to a mixed solvent containing G1 (Figure S5a). Similar PXRD patterns for G1@SAOF-1 and the pristine SAOF-1 revealed the structure of SAOF-1 to be very stable even after substantial loading with fluorophore G1 (Figure S6). Meanwhile, a comparative adsorption experiment revealed that the amorphous Q[10] could not effectively adsorb G1

under the same conditions over different periods, and no fluorescence emission was observed (Figure S5b). This indicated that the guest adsorption ability of SAOF-1 is a function of the properties that arise from the nature of the extended framework as a whole, rather than from an individual Q[10] host.19,20

Figure 4. (a) A preparation process of the microcrystal SAOFbased solid-state fluorescent materials; (b) the structures of the microcrystal SAOF-1, G1, G2 and G3; and (c) the comparison of the colours of SAOF-1, G1, G2, G3, G1@SAOF-1, G2@SAOF-1 and G3@SAOF-1 under day light and UV-light (365 nm); (d) fluorescence spectra of solid G1 and G1@SAOF-1 (λexc =530 nm); (e) fluorescence spectra of solid G2 and G2@SAOF-1 (λexc =340 nm); (f) fluorescence spectra of solid G3 and G3@SAOF-1 (λexc =340 nm).

Based on the G1 adsorption experiments on SAOF-1, similar adsorption experiments on SAOF-1 with the other two selected fluorophore guests G2 and G3, were carried out under the same conditions. G2@SAOF-1 exhibited a pale-white color under daylight, but an interestingly green fluorescence (λmax=485 nm) was significantly observed in its solid-state fluorescence spectrum with excitation wavelength at 340 nm at room temperature (Figure 4e). This emission could be characterized as an excimer emission of the pyrene moiety of G2. In other words, the fluorescence spectra indicated that the pillared diamond shaped SAOF-1 has sufficient pore volume to simultaneously accommodate two and more G2 molecules in the inner cavity of the Q[10] and/or in the extrinsic nanochannels stacked by the outer-surface interactions of Q[10] to form π‒π interactions. Otherwise, the monomer emission of the pyrene moiety with a maximum intensity peak at around 400 nm would have appeared in the spectra.68 Similarly, solid G3@SAOF-1 exhibited a yellow color under daylight, whereas an impressive blue fluorescence emission with a maximum intensity peak at around 465 nm was observed in the fluorescence spectra (Figure 4f). Overall, Figure 4 shows the detailed experimental processes and the optical-properties of all the relevant compounds under daylight and UV light. One can see that the guest dyes G1, G2, and G3 showed only weak fluorescence emissions in the solid state due to the ACQ



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

effect including a physical mixture of the different dye materials with Q[10] in solid state (Figure S7). However, a series of intense fluorescence emissions was elicited from these guest dyes after their uptake by SAOF-1, and the quantum yields of G1, G2, and G3 were estimated to increase from 2.3%, 2.8%, and 1.2% to 13.3%, 52.5%, and 19.5% (the absolute fluorescence quantum yields (Φf(abs)) were measured using a Hamamatsu absolute PL quantum yield spectrometer C11347 Quantaurus_QY), respectively, indicating that the macrocycle-based SAOF-1 not only adopts a novel structure capable of accommodating larger fluorophore, but also has the ability to enhance the emission of these fluorophores in the solid state. Notably, the high quantum yield achieved in SAOF-1 may be attributed to disruption of the ACQ effect on the solid fluorophore by the numerous regular nanopores of SAOF1,69,70 which successfully isolated the relevant fluorophores from one another by loading them in the rigid cavities and channels.

Figure 5. Emission spectra of the mixed G1@SAOF-1, G2@SAOF-1 and G3@SAOF-1 in solid state (λexc =340 nm) with different weight ratio. Inset: white-light emission under UV-light.

The loading capacities of the SAOF-1 were estimated by a 1H NMR technique. Portions (10 mg) of SAOF-1 were added to solutions of the guests (G1 or G2 or G3; 1.0 ×10-2 M) in aliquots (0.5 mL) of mixed solvent (Vdeuterated water/Vdeuterated acetonitrile = 1/9) containing TMS as an internal reference. The changes in the resonances of the guests before and after absorption could then be monitored (Figure S8). The experimental results revealed that the loading capacities of SAOF-1 were about 2.6×10-4 mol·g-1, 3.8×10-4 mol·g-1, and 2.4×10-4 mol·g-1 for G1–G3, respectively. It should be noted that the solid-state fluorescent materials were stable in the ambient environment. Optical stability experiments showed that the solids G1@SAOF-1, G2@SAOF-1, and G3@SAOF-1 could be left to stand in air at room temperature for over six months with no discernible change in their fluorescence. The solid G1@SAOF-1 even showed no change after keeping it under vacuum (ca. 10−1 Pa) at 60 °C for 3 h (Figure S9). Thermal analysis implied that the stability of

Page 4 of 8

G1–G3 could be attributed to the formation of solid G@SAOF-1 (Figure S10-S11). To date, although organic fluorescent materials have been proposed for the fabrication of organic light-emitting diodes (OLEDs), because of their intrinsic photo-oxidative and thermal instability, they do not yet meet the requirements of commercial standards. Therefore, the macrocycle-based supramolecular framework presented herein may represent a new concept for the fabrication of thermally stable OLEDs. After much effort, we identified three suitable organic dyes, G1, G2, and G3, and prepared three solid-state fluorescent materials, G1@SAOF-1, G2@SAOF-1, and G3@SAOF-1, showing red, green, and blue (RGB) fluorescence emissions, respectively. In the course of this work, we noted that both the green (λmax =485 nm) and blue emissions (λmax =465 nm) of G2@SAOF-1 and G3@SAOF-1 could be independently obtained at an excitation wavelength of 340 nm, further leading to partial spectral overlap between the emissions and absorption of G1@SAOF-1 (Figure S12). This indicated that they could act as a donor– acceptor couple for partial excitation energy transfer.71 Thus, the green and blue emissions were used as the donor fluorophore and G1@SAOF-1 (λmax(absorption) =538 nm) with red fluorescence (λmax(emission) =608 nm) was used as the acceptor. Hence, at a certain mixing weight ratio of G1@SAOF-1, G2@SAOF-1, and G3@SAOF-1, a white emission should be obtained from the solid upon excitation of the energy donor based on the RGB emitting principle. Figure 5 shows the fluorescence spectra of solid mixtures of G1@SAOF-1, G2@SAOF-1, and G3@SAOF-1 upon excitation at 340 nm. The RGB mixture without the G1@SAOF-1 acceptor retained the blue and green emissions. The mixed solid showed a gradual decrease in the donor emission in the region 430–550 nm and a concomitant increase in the acceptor (G1@SAOF-1) emission at 608 nm, with increasing acceptor loading weight. Since the acceptor absorbs much less strongly at the excitation wavelength of 340 nm (Figure S13), the appearance of the red emission from the mixed solid is clearly due to the energytransfer process. Remarkably, with a 44% weight loading of the acceptor, the mixed solid showed white-light emission, as evident from CIE coordinates of (0.32, 0.28). In summary, we have demonstrated a simple method for the synthesis of a novel Q[10]-[Cd4Cl16]8–-based porous supramolecular framework by simply mixing Q[10] and CdCl2 in aqueous HCl at room temperature. Its topological structure shows a 3D open-nanotube-based pillared diamond framework, assembled through the outer-surface interactions of Q[10], which are different from those existing in Q[n]-based MOFs, SOFs, or COFs. Therefore, we tentatively refer to it as a Q[10]-based supramolecular inorganic anion–organic framework (SAOF). Moreover, this Q[10]-based SAOF can effectively adsorb various organic dyes to yield multi-emitting, including white-light-emitting, solid fluorescent materials with high quantum yield and good thermal stability. This study might therefore open up new Q[n]-based SAOF chemistry in the fields of porous


Page 5 of 8

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


materials and light-emitters. More extensive investigations on the Q[n]-based SAOFs and their functions are currently underway.

ASSOCIATED CONTENT Supporting Information. Experimental procedure, Video, Crystal data, PXRD patterns, Titration 1H NMR spectra, Thermal analysis, Fluorescence spectra and so on.

AUTHOR INFORMATION Corresponding Author

[email protected] (X.-L. Ni) and [email protected] (G. Wei) Author Contributions Yu-Qing Yao and Ying-Jie Zhang contributed equally.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21361006, 51463004), “Chun-Hui” Fund of Chinese Ministry of Education (Z2016011), the Science and Technology Talent Fund of Guizhou Province (20165656), and the Graduate Student’s Fund for innovation of Guizhou University (2017008). The single crystal data for SAOF-1 was collected on the MX beamlines at the Australian Synchrotron, Victoria, Australia.

REFERENCES (1) D’Alessandro, D. M.; Smit, B.; Long, J. R. Carbon Dioxide Capture: Prospects for New Materials. Angew. Chem., Int. Ed. 2010, 49, 6058-6082. (2) Getman, R. B.; Bae, Y. S.; Wilmer, C. E.; Snurr, R. Q. Review and Analysis of Molecular Simulations of Methane, Hydrogen, and Acetylene Storage in Metal–Organic Frameworks. Chem. Rev. 2012, 112, 703-723. (3) Howarth, A. J.; Peters, A. W.; Vermeulen, N. A.; Wang, T. C.; Hupp, J. T.; Farha, O. K. Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks, Chem. Mater. 2017, 29, 26–39. (4) Lin, Y.; Jiang, X.; Kim, S. T.; Alahakoon, S. B.; Hou, X.; Zhang, Z.; Thompson, C. M.; Smaldone, R. A.; Ke, C. An Elastic Hydrogen-bonded Crosslinked Organic Framework for Effective Iodine Capture in Water. J. Am. Chem. Soc. 2017, 139, 7172-7175. (5) Liao, P. Q.; Huang, N. Y.; Zhang, W. X.; Zhang, J. P.; Chen, X. M. Controlling Guest Conformation for Efficient Purification of Butadiene. Science 2017, 356, 1193-1196. (6) Ding, S.; Gao, J.; Wang, Q.; Zhang, Y.; Song, W.; Su, C.; Wang, W. Construction of Covalent Organic Framework for Catalysis: Pd/COF-LZU1 in Suzuki–Miyaura Coupling Reaction. J. Am. Chem. Soc. 2011, 133, 19816-19822. (7) Xu, H.; Gao, J.; Jiang, D. Stable, Crystalline, Porous, Covalent Organic Frameworks as A Platform for Chiral Organocatalysts. Nat. Chem. 2015, 7, 905-912. (8) Wang, X.; Han, X.; Zhang, J.; Wu, X.; Liu, Y.; Cui, Y. Homochiral 2D Porous Covalent Organic Frameworks for Heterogeneous Asymmetric Catalysis. J. Am. Chem. Soc. 2016, 138, 12332-12335. (9) Wu, M. X.; Yang, Y. W. Metal−organic Framework (MOF)Based Drug/Cargo Delivery and Cancer Therapy. Adv. Mater. 2017, 29, 1606134-1606134. (10) Fang, Q.; Wang, J.; Gu, S.; Kaspar, R. B.; Zhuang, Z.; Zheng, J.; Guo, H.; Qiu, S.; Yan, Y. 3D Porous Crystalline Polyimide

Covalent Organic Frameworks for Drug Delivery. J. Am. Chem. Soc. 2015, 137, 8352-8355. (11) DeBlase, C. R.; Silberstein, K. E.; Truong, T. T.; Abruña, H. D.; Dichtel, W. R. β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage J. Am. Chem. Soc. 2013, 135, 16821-16824. (12) Bertrand, G. H.; Michaelis, V. K.; Ong, T. C.; Griffin, R. G.; Dincă, M. Thiophene-Based Covalent Organic Frameworks. Proc. Natl. Acad. Sci. U. S. A. 2013, 110, 4923-4928. (13) Wang, L.; Han, Y.; Feng, X.; Zhou, J.; Qi, P.; Wang, B. Metal–Organic Frameworks for Energy Storage: Batteries and Supercapacitors. Coord. Chem. Rev. 2016, 307, 361-381. (14) Du, Y.; Yang, H.; Whiteley, J. M.; Wan, S.; Jin, Y.; Lee, S. H.; Zhang, W. Ionic Covalent Organic Frameworks with Spiroborate Linkage Angew. Chem., Int. Ed. 2016, 55, 1737-1741. (15) Vazquez-Molina, D. A.; Mohammad-Pour, G. S.; Lee, C.; Logan, M. W.; Duan, X.; Harper, J. K.; Uribe-Romo, F. J. Mechanically Shaped Two-Dimensional Covalent Organic Frameworks Reveal Crystallographic Alignment and Fast Li-Ion Conductivity. J. Am. Chem. Soc. 2016, 138, 9767-9770. (16) Atwood, J. L.; Barbour, L. J.; Jerga, A.; Schottel, B. L. Guest Transport in a Nonporous Organic Solid via Dynamic van der Waals Cooperativity. Science 2002, 298, 1000-1002. (17) Zhang, Z.; Drapailo, A.; Matvieiev, Y.; Wojtas, L.; Zaworotko, M. J. A Calixarene Based Metal Organic Material, CalixMOM, that Binds Potassium Cations. Chem. Commun. 2013, 49, 8353-8355. (18) Pei, W. Y.; Xu, G.; Yang, J.; Wu, H.; Chen, B.; Zhou, W.; Ma, J. F. Versatile Assembly of Metal-Coordinated Calix [4] Resorcinarene Cavitands and Cages through Ancillary Linker Tuning. J. Am. Chem. Soc. 2017, 139, 7648-7656. (19) Hartlieb, K. J.; Holcroft, J. M.; Moghadam, P. Z.; Vermeulen, N. A.; Algaradah, M. M.; Nassar, M. S.; Botros, Y. Y.; Snurr, R. Q.; Stoddart, J. F. CD-MOF: A Versatile Separation Medium. J. Am. Chem. Soc. 2016, 138, 2292-2301. (20) Smaldone, R. A.; Forgan, R. S.; Furukawa, H.; Gassensmith, J. J.; Slawin, A. M. Z.; Yaghi, O. M.; Stoddart, J. F. Metal–Organic Frameworks from Edible Natural Products. Angew. Chem., Int. Ed. 2010, 49, 8630-8634. (21) Lim, S.; Kim, H.; Selvapalam, N.; Kim, K. J.; Cho, S. J.; Seo, G.; Kim, K. Cucurbit [6] uril: Organic Molecular Porous Material with Permanent Porosity, Exceptional Stability, and Acetylene Sorption Properties. Angew. Chem., Int. Ed. 2008, 47, 3352-3355. (22) Kim, H.; Kim, Y.; Yoon, M.; Lim, S.; Park, S. M.; Seo, G.; Kim, K. Highly Selective Carbon Dioxide Sorption in An Organic Molecular Porous Material. J. Am. Chem. Soc. 2010, 132, 1220012202. (23) Fang, X. K.; Kogerler, P.; Isaacs, L.; Uchida, S.; Mizuno, N. Cucurbit[n]uril−Polyoxoanion Hybrids. J. Am. Chem. Soc. 2009, 131, 432-433. (24) Tian, J.; Liu, J.; Liu, J.; Thallapally, P. K. Identification of Solid-State Forms of Cucurbit[6]uril for Carbon Dioxide Capture. CrystEngComm 2013, 15, 1528-1531. (25) Tian, J.; Ma, S.; Thallapally, P. K.; Fowler, D.; McGrail, B. P.; Atwood, J. L. Cucurbit[7]uril: an Amorphous Molecular Material for Highly Selective Carbon Dioxide Uptake. Chem. Commun. 2011, 47, 7626-7628. (26) Wang, P.; Wu, Y.; Zhao, Y.; Yu, Y.; Zhang, M.; Cao, L. Crystalline Nanotubular Framework Constructed by Cucurbit[8]uril for Selective CO2 Adsorption. Chem. Commun. 2017, 53, 5503-5506. (27) Ji, N. N.; Cheng, X. J.; Zhao, Y.; Liang, L. L.; Ni, X. L.; Xiao, X.; Zhu, Q. J.; Xue, S. F.; Dong, N.; Tao, Z. Tetrachloridometallate Dianion-Induced Cucurbit[8]uril Supramolecular Assemblies with Large Channels and Their Potential Applications for Extraction Coating on Solid-Phase Microextraction Fibers. Inorg. Chem. 2014, 53, 21-23. (28) Li, Q.; Qiu, S.-C.; Zhang, Y.-Q.; Xue, S.-F.; Tao, Z.; Prior, T. J.; Redshaw, C.; Zhu, Q.-J.; Xiao, X. Supramolecular Assemblies Constructed from Inverted Cucurbit[7]uril and Lanthanide Cations:



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

Synthesis, Structure and Sorption Properties. RSC Adv. 2016, 6, 77805-77810. (29) Jie, K.; Liu, M.; Zhou, Y.; Little, M. A.; Bonakala, S.; Chong, S. Y.; Stephenson, A.; Chen, L.; Huang, F.; Cooper, A. I. Styrene Purification by Guest-Induced Restructuring of Pillar[6]arene. J. Am. Chem. Soc. 2017, 139, 2908-2911. (30) Tan, L. L.; Zhu, Y.; Long, H.; Jin, Y.; Zhang, W.; Yang, Y. W. Pillar[n]arene-Based Supramolecular Organic Frameworks with High Hydrocarbon Storage and Selectivity. Chem. Commun. 2017, 53, 6409-6412. (31) Tan, L. L.; Li, H.; Tao, Y.; Zhang, S. X. A.; Wang, B.; Yang, Y. W. Pillar [5] arene-Based Supramolecular Organic Frameworks for Highly Selective CO2-Capture at Ambient Conditions. Adv. Mater. 2014, 26, 7027-7031. (32) Day, A. I.; Arnold, A. P. WO 0068232, 2000, p8. (33) Day, A. I.; Arnold, A. P.; Blanch, R. J.; Snushall, B. Controlling Factors in the Synthesis of Cucurbituril and Its Homologues. J. Org. Chem. 2001, 66, 8094-8100. (34) Kim, J.; Jung, I. S.; Kim, S. Y.; Lee, E.; Kang, J. K.; Sakamoto, S.; Yamaguchi, K.; Kim, K. New Cucurbituril Homologues: Syntheses, Isolation, Characterization, and X-ray Crystal Structures of Cucurbit[n]uril (n = 5, 7, and 8). J. Am. Chem. Soc. 2000, 122, 540-541. (35) Lee, J. W.; Samal, S.; Selvapalam, N.; Kim, H. J.; Kim, K. Cucurbituril Homologues and Derivatives: New Opportunities in Supramolecular Chemistry. Acc. Chem. Res. 2003, 36, 621-630. (36) Lagona, J.; Mukhopadhyay, P.; Chakrabarti, S.; Isaacs, L. The Cucurbit[n]uril Family. Angew. Chem., Int. Ed. 2005, 44, 4844-4870. (37) Masson, E.; Ling, X.; Joseph, R.; Kyeremeh-Mensah, L.; Lu, X. Cucurbituril Chemistry: a Tale of Supramolecular Success. RSC Adv. 2012, 2, 1213-1247. (38) Barrow, S. J.; Kasera, S.; Rowland, M. J.; del Barrio, J.; Scherman, O. A. Cucurbituril-Based Molecular Rrecognition. Chem. Rev. 2015, 115, 12320-12406. (39) Assaf, K. I.; Nau, W. M. Cucurbiturils: From Synthesis to High-Affinity Binding and Catalysis. Chem. Soc. Rev. 2015, 44, 394418. (40) Ni, X. L.; Xiao, X.; Cong, H.; Zhu, Q. J.; Xue, S. F.; Tao, Z. Self-Assemblies Based on The “Outer-Surface Interactions” of Cucurbit[n]urils: New Opportunities for Supramolecular Architectures and Materials. Acc. Chem. Res. 2014, 47, 1386-1395. (41) Chen, K.; Kang, Y. S.; Zhao, Y.; Yang, J. M.; Lu, Y.; Sun, W. Y. Cucurbit[6]uril-Based Supramolecular Assemblies: Possible Appli-cation in Radioactive Cesium Cation Capture. J. Am. Chem. Soc. 2014, 136, 16744-16747. (42) Zhang, Y.; Zhan, T. G.; Zhou, T. Y.; Qi, Q. Y.; Xu, X. N.; Zhao, X. Fluorescence Enhancement through the Formation of a Single-Layer Two-Dimensional Supramolecular Organic Framework and Its Application in Highly Selective Recognition of Picric Acid. Chem.Commun. 2016, 52, 7588-7591. (43) Lin, J. X.; Liang, J.; Feng, J. F.; Karadeniz, B.; Lü, J.; Cao, R. Iodine Uptake and Enhanced Electrical Conductivity in A Porous Coordination Polymer Based on Cucurbit[6]uril. Inorg. Chem. Front. 2016, 3, 1393-1397. (44) Goel, T.; Barooah, N.; Mallia, M. B.; Bhasikuttan, A. C.; Mohanty, J. Recognition-Mediated Cucurbit[7]uril-Heptamolybdate Hybrid Material: A Facile Supramolecular Strategy for 99m Tc Separation. Chem. Commun. 2016, 52, 7306-7309. (45) Cui, X. W.; Zhao, W. X.; Chen, K.; Ni, X. L.; Zhang, Y. Q.; Tao, Z. Outer Surface Interactions of Cucurbit[6]uril That Trigger the As-sembly of Supramolecular Three-Dimensional Polycatenanes. Chem. Eur. J. 2017, 23, 2759-2763. (46) Yao, Y. Q.; Zhang, Y. J.; Huang, C.; Zhu, Q. J.; Tao, Z.; Ni, X. L.; Wei, G. Cucurbit[10]uril-Based Smart Supramolecular Organic Frameworks in Selective Isolation of Metal Cations. Chem. Mater. 2017, 29, 5468-5472. (47) Liang, L. L.; Ni, X. L.; Zhao, Y.; Chen, K.; Xiao, X.; Zhang, Y. Q.; Redshaw, C.; Zhu, Q. J.; Xue, S. F.; Tao, Z. Construction of

Page 6 of 8

Cucurbit[7]uril Based Tubular Nanochannels Incorporating Associated [CdCl4]2- and Lanthanide. Ions Inorg. Chem. 2013, 52, 1909-1915. (48) Ni, X. L.; Xiao, X.; Cong, H.; Liang, L. L.; Cheng, K.; Cheng, X. J.; Ji, N. N.; Zhu, Q. J.; Xue, S. F.; Tao, Z. Cucurbit[n]uril-Based Coordination Chemistry: From Simple Coordination Complexes to Novel Poly-Dimensional Coordination Polymers. Chem. Soc. Rev. 2013, 42, 9480-9508. (49) Ni, X. L.; Xue, S. F.; Tao, Z.; Zhu, Q. J.; Lindoy, L. F.; Wei, G. Advances in The Lanthanide Metallosupramolecular Chemistry of The Cucurbit[n]urils. Coord. Chem. Rev. 2015, 287, 89-113. (50) Yao, Y. Q.; Liu, Q.; Huang, Y.; Zhu, Q. J.; Zhang, Y. Q.; Xiao, X.; Tao, Z.; Wei, G. Supramolecular Assemblies of Cucurbit [10] uril Based on Outer Surface Interactions. Aust. J. Chem. 2017, 70, 637641. (51) Yan, X.; Cook, T. R.; Wang, P.; Huang, F.; Stang, P. J. Highly Emissive Platinum(II) Metallacages. Nat. Chem. 2015, 7, 342-348. (52) Xu, L.; Wang, Y. X.; Yang, H. B. Recent Advances in The Construction of Fluorescent Metallocycles and Metallocages via Coordination-Driven Self-Assembly. Dalton Trans. 2015, 44, 867890. (53) Frischmann, P. D.; Kunz, V.; Würthner, F. Bright Fluorescence and Host-Guest Sensing with a Nanoscale M4L6 Tetrahedron Accessed by Self-Assembly of Zinc-Imine Chelate Vertices and Perylene Bisimide Edges. Angew. Chem., Int. Ed. 2015, 54, 7285-7289. (54) Yamashina, M.; Sartin, M. M.; Sei, Y.; Akita, M.; Takeuchi, S.; Tahara, T.; Yoshizawa, M. Preparation of Highly Fluorescent Host–Guest Complexes with Tunable Color upon Encapsulation. J. Am. Chem. Soc. 2015, 137, 9266-9269. (55) Ni, X. L.; Chen, S. Y.; Yang, Y.; Tao, Z. Facile Cucurbit[8]uril-Based Supramolecular Approach To Fabricate Tunable Luminescent Materials in Aqueous Solution. J. Am. Chem. Soc. 2016, 138, 6177-6183. (56) Wang, H.; Ji, X.; Li, Z.; Huang, F. Fluorescent Supramolecular Polymeric Materials. Adv. Mater. 2017, 29, 1606117l. (57) Xu, Z.; Peng, S.; Wang, Y. Y.; Zhang, J. K.; Lazar, A. I.; Guo, D. S. Broad-Spectrum Tunable Photoluminescent Nanomaterials Constructed from a Modular Light-Harvesting Platform Based on Macrocyclic Amphiphiles. Adv. Mater. 2016, 28, 7666-7671. (58) Zhang, Q.W.; Li, D. F.; Li, X.; White, P. B.; Mecinovic, J.; Ma, X.; Agren, H.; Nolte, R. J. M.; Tian, H. Multicolor Photoluminescence Including White-Light Emission by a Single Host-Guest Complex. J. Am. Chem. Soc. 2016, 138, 13541-13550. (59) Fan, C.; Wu, W.; Chruma, J. J.; Zhao, J.; Yang, C. Enhanced Triplet-Triplet Energy Transfer and Upconversion Fluorescence through Host-Guest Complexation. J. Am. Chem. Soc. 2016, 138, 15405-15412. (60) Jiao, Y.; Li, W. L.; Xu, J. F.; Wang, G.; Li, J.; Wang, Z.; Zhang, X. A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation. Angew. Chem., Int. Ed. 2016, 55, 8933-8937. (61) Fang, Q. R.; Zhu, G. S.; Jin, Z.; Ji, Y. Y.; Ye, J. W.; Xue, M.; Yang, H.; Wang, Y.; Qiu, S. L. Mesoporous Metal-Organic Framework with Rare Etb Topology for Hydrogen Storage and Dye Assembly. Angew. Chem., Int. Ed. 2007, 46, 6638-6642. (62) Wang, J.; He, C.; Wu, P.; Wang, J.; Duan, C. An AmideContaining Metal-Organic Tetrahedron Responding to a SpinTrapping Reaction in a Fluorescent Enhancement Manner for Biological Imaging of NO in Living Cells. J. Am. Chem. Soc. 2011, 133, 12402-12405. (63) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Luminescent Functional Metal-Organic Frameworks. Chem. Rev. 2012, 112, 1126-1162. (64) Wen, Y.; Sheng, T.; Zhu, X.; Zhuo, C.; Su, S.; Li, H.; Hu, S.; Zhu, Q.-L.; Wu X. Introduction of Red-Green-Blue Fluorescent Dyes into a Metal–Organic Framework for Tunable White Light Emission. Adv. Mater. 2017, 29, 1700778.


Page 7 of 8

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


(65) Day, A. I.; Blanch, R. J.; Arnold, A. P.; Lorenzo, S.; Lewis, G. R.; Dance, I. A. A Cucurbituril-Based Gyroscane: A New Supramolecular Form. Angew. Chem., Int. Ed. 2002, 41, 275-277. (66) Liu, S.; Zavalij, P. Y.; Isaacs, L. Cucurbit [10] uril. J. Am. Chem. Soc. 2005, 127, 16798-16799. (67) Dsouza, R. N.; Pischel, U.; Nau, W. M. Fluorescent Dyes and Their Supramolecular Host/Guest Complexes with Macrocycles in Aqueous Solution. Chem. Rev. 2011, 111, 7941-7980. (68) Feng, X.; Hu, J.-Y.; Redshaw, C.; Yamato T. Functionalization of Pyrene To Prepare Luminescent MaterialsTypical Examples of Synthetic Methodology. Chem. Eur. J. 2016, 22, 11898-11916. (69) Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Aggregation-Induced Emission. Chem. Soc. Rev. 2011, 40, 5361-5388. (70) Mei, J.; Hong, Y.; Lam, J. W. Y.; Qin, A.; Tang, Y.; Tang, B. Z. Aggregation-Induced Emission: The Whole Is More Brilliant than the Parts. Adv. Mater. 2014, 26, 5429-5479. (71) Abbel, R.; Grenier, C.; Pouderoijen, M. J.; Stouwdam, J. W.; Leclère, P. E. L. G.; Sijbesma, R. P.; Meijer, E. W.; Schenning, A. P. H. J. White-Light Emitting Hydrogen-Bonded Supramolecular Copolymers Based on π-Conjugated Oligomers. J. Am. Chem. Soc. 2009, 131, 833-843.



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

For Table of Contents


Page 8 of 8

Multiple Efficient Fluorescence Emission from Cucurbit[10]uril

Recommend Documents