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Journal articles on the topic 'Truxene based supramolecular cages'

Author: Grafiati

Published: 28 March 2023

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1

Benchohra, Amina, Simon Séjourné, Antoine Labrunie, Liam Miller, Enzo Charbonneau, Vincent Carré, Frédéric Aubriet, Magali Allain, Marc Sallé, and Sébastien Goeb. "Controlling Chiral Self-Sorting in Truxene-Based Self-Assembled Cages." Inorganics 10, no. 7 (July 19, 2022): 103. http://dx.doi.org/10.3390/inorganics10070103.

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Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M2), afforded three chiral face-rotating stereoisomer polyhedra (M6L2). By tuning the length of the alkyl chains as well as the distance between both ligands facing each other in the self-assemblies (M6L2), one can control the diastereomeric distribution between the expected homo- and hetero-chiral structures.

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2

Raee, Ehsan, Yuqing Yang, and Tianbo Liu. "Supramolecular structures based on metal-organic cages." Giant 5 (March 2021): 100050. http://dx.doi.org/10.1016/j.giant.2021.100050.

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3

Ling, Qing-Hui, Jun-Long Zhu, Yi Qin, and Lin Xu. "Naphthalene diimide- and perylene diimide-based supramolecular cages." Materials Chemistry Frontiers 4, no. 11 (2020): 3176–89. http://dx.doi.org/10.1039/d0qm00540a.

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4

Kniazeva, Mariia V., Alexander S. Ovsyannikov, Aida I. Samigullina, Daut R. Islamov, Aidar T. Gubaidullin, Pavel V. Dorovatovskii, Vladimir A. Lazarenko, Svetlana E. Solovieva, Igor S. Antipin, and Sylvie Ferlay. "Impact of flexible succinate connectors on the formation of tetrasulfonylcalix[4]arene based nano-sized polynuclear cages: structural diversity and induced chirality study." CrystEngComm 24, no. 3 (2022): 628–38. http://dx.doi.org/10.1039/d1ce01482j.

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The formation of three types of supramolecular coordination cages is described. Tetrasulfonylcalixarene, combined with metallic salts (Ni, Co and Zn) and the flexible succinate ligand, led to cages. H bonded induced chirality was observed for both isomorphous cages.

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5

Yadav, Sarita, Palanisamy Kannan, and Guanyinsheng Qiu. "Cavity-based applications of metallo-supramolecular coordination cages (MSCCs)." Organic Chemistry Frontiers 7, no. 18 (2020): 2842–72. http://dx.doi.org/10.1039/d0qo00681e.

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This review describes cavity-based applications of cage-like SCCs such as molecular recognition and separation, stabilization of reactive species by encapsulation, as drug delivery systems and as molecular flasks.

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Zhang, Hai-Xia, Xiaodong Yan, Yu-Xin Chen, Shu-Heng Zhang, Tao Li, Wang-Kang Han, Ling-Yu Bao, Rui Shen, and Zhi-Guo Gu. "A zeolite supramolecular framework with LTA topology based on a tetrahedral metal–organic cage." Chemical Communications 55, no. 8 (2019): 1120–23. http://dx.doi.org/10.1039/c8cc08965e.

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7

Decker, Gerald E., Gregory R. Lorzing, Meaghan M. Deegan, and Eric D. Bloch. "MOF-mimetic molecules: carboxylate-based supramolecular complexes as molecular metal–organic framework analogues." Journal of Materials Chemistry A 8, no. 8 (2020): 4217–29. http://dx.doi.org/10.1039/c9ta12497g.

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8

Taylor, Christopher G. P., Jerico R. Piper, and Michael D. Ward. "Binding of chemical warfare agent simulants as guests in a coordination cage: contributions to binding and a fluorescence-based response." Chemical Communications 52, no. 37 (2016): 6225–28. http://dx.doi.org/10.1039/c6cc02021f.

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9

Lu, Hui-Shu, Wang-Kang Han, Xiaodong Yan, Ya-Xin Xu, Hai-Xia Zhang, Tao Li, Yu Gong, Qing-Tao Hu, and Zhi-Guo Gu. "Supramolecular assemblies based on Fe8L12 cubic metal–organic cages: synergistic adsorption and spin-crossover properties." Dalton Transactions 49, no. 14 (2020): 4220–24. http://dx.doi.org/10.1039/d0dt00353k.

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10

Liu, Wen-Fang, Qi-Ming Qiu, Mo Zhang, Zhao-Min Su, Qingqing An, Hongjin Lv, Zhiyu Jia, and Guo-Yu Yang. "Two new Cu-based borate catalysts with cubic supramolecular cages for efficient catalytic hydrogen evolution." Dalton Transactions 49, no. 29 (2020): 10156–61. http://dx.doi.org/10.1039/d0dt01994a.

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Two new copper-based borates with supramolecular cages were synthesized under hydrothermal condition. As new copper complexes, they exhibit photocatalytic activity. The experimental results show borates have potential applications as water reduction catalysts (WRCs).

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11

Gu, Meng-Jie, Yin-Feng Wang, Ying Han, and Chuan-Feng Chen. "Recent advances on triptycene derivatives in supramolecular and materials chemistry." Organic & Biomolecular Chemistry 19, no. 46 (2021): 10047–67. http://dx.doi.org/10.1039/d1ob01818c.

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12

Yang, Jiajia, Mohan Bhadbhade, William A. Donald, Hasti Iranmanesh, Evan G. Moore, Hong Yan, and Jonathon E. Beves. "Self-assembled supramolecular cages containing ruthenium(ii) polypyridyl complexes." Chemical Communications 51, no. 21 (2015): 4465–68. http://dx.doi.org/10.1039/c4cc10292d.

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Substitution-inert, redox- and photo-active ruthenium(ii) complexes based on 2,2′,6′,2′′-terpyridine ligands were self-assembled into discrete supramolecular cages via coordination to palladium(ii) centres and characterised by NMR, ESI-MS and X-ray crystallography.

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13

Jana, Atanu, Steffen Bähring, Masatoshi Ishida, Sébastien Goeb, David Canevet, Marc Sallé, Jan O. Jeppesen, and Jonathan L. Sessler. "Functionalised tetrathiafulvalene- (TTF-) macrocycles: recent trends in applied supramolecular chemistry." Chemical Society Reviews 47, no. 15 (2018): 5614–45. http://dx.doi.org/10.1039/c8cs00035b.

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Tetrathiafulvalene- (TTF-) based macrocyclic systems, cages and supramolecularly self-assembled 3D constructs have been extensively explored as functional materials for sensing and switching applications.

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14

Struch, N., F. Topić, K. Rissanen, and A. Lützen. "Electron-deficient trifluoromethyl-substituted sub-components affect the properties of M4L4 tetrahedral cages." Dalton Transactions 46, no. 33 (2017): 10809–13. http://dx.doi.org/10.1039/c7dt02182h.

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15

Bao, Shu-Jin, Ze-Ming Xu, Tian-Chen Yu, Ying-Lin Song, Heng Wang, Zheng Niu, Xiaopeng Li, Brendan F. Abrahams, Pierre Braunstein, and Jian-Ping Lang. "Flexible Vertex Engineers the Controlled Assembly of Distorted Supramolecular Tetrahedral and Octahedral Cages." Research 2022 (February 24, 2022): 1–12. http://dx.doi.org/10.34133/2022/9819343.

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Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.

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16

Li, LiLi, Linlin Yang, Xuezhao Li, Jing Wang, Xin Liu, and Cheng He. "Supramolecular Catalysis of Acyl Transfer within Zinc Porphyrin-Based Metal–Organic Cages." Inorganic Chemistry 60, no. 12 (June 4, 2021): 8802–10. http://dx.doi.org/10.1021/acs.inorgchem.1c00745.

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17

Bravin, Carlo, Elena Badetti, Rakesh Puttreddy, Fangfang Pan, Kari Rissanen, Giulia Licini, and Cristiano Zonta. "Binding Profiles of Self-Assembled Supramolecular Cages from ESI-MS Based Methodology." Chemistry - A European Journal 24, no. 12 (January 31, 2018): 2936–43. http://dx.doi.org/10.1002/chem.201704725.

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18

Chen, Shi-Gui, Zhi-Xiong Zhao, Xiao-Nan Jiang, Lu Wang, Tian-You Zhou, Cheng-Lu Lu, Xin Zhao, et al. "Temperature-Responsive Chiral (A)6 B Supramolecular Cages Based on Conformational Preferences." Chemistry - An Asian Journal 11, no. 4 (November 25, 2015): 465–69. http://dx.doi.org/10.1002/asia.201501090.

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19

Kuang, Xiaofei, Shanci Chen, Lingyi Meng, Jing Chen, Xiaoyuan Wu, Guanhua Zhang, Guiming Zhong, Ting Hu, Yuhang Li, and Can-Zhong Lu. "Supramolecular aggregation of a redox-active copper-naphthalenediimide network with intrinsic electron conduction." Chemical Communications 55, no. 11 (2019): 1643–46. http://dx.doi.org/10.1039/c8cc10269d.

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20

Liu, Die, Haisheng Liu, Bo Song, Mingzhao Chen, Jian Huang, Jun Wang, Xiaoyu Yang, Wei Sun, Xiaopeng Li, and Pingshan Wang. "Terpyridine-based metallo-organic cages and supramolecular gelation by coordination-driven self-assembly and host–guest interaction." Dalton Transactions 47, no. 40 (2018): 14227–32. http://dx.doi.org/10.1039/c8dt01044g.

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21

Kumar, Atul, Rupak Saha, and Partha Sarathi Mukherjee. "Self-assembled metallasupramolecular cages towards light harvesting systems for oxidative cyclization." Chemical Science 12, no. 14 (2021): 5319–29. http://dx.doi.org/10.1039/d1sc00097g.

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Synthesis of Pt(ii) based metallacages as aggregation induced emissive supramolecular architectures for fabricating artificial light harvesting systems for cross coupling cyclization under visible light is achieved.

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22

Rivera, Daniel G., and Ludger A. Wessjohann. "Supramolecular Compounds from Multiple Ugi Multicomponent Macrocyclizations: Peptoid-based Cryptands, Cages, and Cryptophanes." Journal of the American Chemical Society 128, no. 22 (June 2006): 7122–23. http://dx.doi.org/10.1021/ja060720r.

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23

Li, Na, Xue-Na Yin, and Ru-Dan Huang. "Encapsulation of polyoxometalates into supramolecular cages based on flexible ligands: Synthesis, structure and properties." Inorganica Chimica Acta 429 (April 2015): 216–20. http://dx.doi.org/10.1016/j.ica.2015.02.009.

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24

Sun, Na, Shi‐Qiang Wang, Yassin H. Andaloussi, Guorui Liu, Tonghuan Fu, Jialiang Xu, Michael J. Zaworotko, and Xian‐He Bu. "Supramolecular Cages Based on a Silver Complex as Adaptable Hosts for Poly‐Aromatic Hydrocarbons." Small 16, no. 47 (November 2020): 2001377. http://dx.doi.org/10.1002/smll.202001377.

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25

Miljkovic, Ana, Sonia La Cognata, Greta Bergamaschi, Mauro Freccero, Antonio Poggi, and Valeria Amendola. "Towards Building Blocks for Supramolecular Architectures Based on Azacryptates." Molecules 25, no. 7 (April 9, 2020): 1733. http://dx.doi.org/10.3390/molecules25071733.

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In this work, we report the synthesis of a new bis(tris(2-aminoethyl)amine) azacryptand L with triphenyl spacers. The binding properties of its dicopper complex for aromatic dicarboxylate anions (as TBA salts) were investigated, with the aim to obtain potential building blocks for supramolecular structures like rotaxanes and pseudo-rotaxanes. As expected, UV-Vis and emission studies of [Cu2L]4+ in water/acetonitrile mixture (pH = 7) showed a high affinity for biphenyl-4,4′-dicarboxylate (dfc2−), with a binding constant of 5.46 log units, due to the best match of the anion bite with the Cu(II)-Cu(II) distance in the cage’s cavity. Compared to other similar bistren cages, the difference of the affinity of [Cu2L]4+ for the tested anions was not so pronounced: conformational changes of L seem to promote a good interaction with both long (e.g., dfc2−) and short anions (e.g., terephthalate). The good affinity of [Cu2L]4+ for these dicarboxylates, together with hydrophobic interactions within the cage’s cavity, may promote the self-assembly of a stable 1:1 complex in water mixture. These results represent a good starting point for the application of these molecular systems as building units for the design of new supramolecular architectures based on non-covalent interactions, which could be of interest in all fields related to supramolecular devices.

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Bravin, Carlo, Andrea Guidetti, Giulia Licini, and Cristiano Zonta. "Supramolecular cages as differential sensors for dicarboxylate anions: guest length sensing using principal component analysis of ESI-MS and 1H-NMR raw data." Chemical Science 10, no. 12 (2019): 3523–28. http://dx.doi.org/10.1039/c8sc05527k.

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27

Vlassa, Mihaela, Gheorghe Borodi, Cristian Silvestru, and Mircea Vlassa. "Hydrogen bonding-based 3D supramolecular architecture of [Cu(CHA)2][TCM]·11H2O." Open Chemistry 12, no. 1 (January 1, 2014): 14–24. http://dx.doi.org/10.2478/s11532-013-0350-0.

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AbstractReaction of Na4TCM (1) (H4TCM = tetra[4-(carboxyphenyl)oxamethyl]methane) with [Cu(CHA)](ClO4)2 (2)(CHA = 1,3,6,8,11,14-hexaaz atricyclo[12.2.1.1.8,11] octadecane) in a DMF-water mixture yields [Cu(CHA)]2[TCM] (3). Structural analysis of [Cu(CHA)]2[TCM]·11H2O (3·11H2O) by single crystal X-ray diffraction reveals strong copper-oxygen bonds between two complex cations and the tetraanion leading to a 3D coordination network (zwitterionic structure), consolidated through additional NH...O=C hydrogen bonding within the cation/anion association. The resulting coordination geometry around a copper atom is a distorted square pyramidal with an oxygen atom of the anionic ligand in the apical position. A 3D supramolecular network is developed in the crystal based only on NH...OC hydrogen bonds between the macrocyclic metallic tecton and the carboxylate groups of neighboring 3D coordinated (zwitterionic) moieties. The pseudotetrahedral TCM4− tetraanionic ligand induces a diamondoid architecture formed of large distorted adamantanoid cages.

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28

Carlotto, Silvia, Lidia Armelao, and Marzio Rancan. "Helicate versus Mesocate in Quadruple-Stranded Lanthanide Cages: A Computational Insight." International Journal of Molecular Sciences 23, no. 18 (September 13, 2022): 10619. http://dx.doi.org/10.3390/ijms231810619.

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To drive the synthesis of metallo-supramolecular assemblies (MSAs) and to fully exploit their functional properties, robust computational tools are crucial. The capability to model and to rationalize different parameters that can influence the outcome is mandatory. Here, we report a computational insight on the factors that can determine the relative stability of the supramolecular isomers helicate and mesocate in lanthanide-based quadruple-stranded assemblies. The considered MSAs have the general formula [Ln2L4]2− and possess a cavity suitable to allocate guests. The analysis was focused on three different factors: the ligand rigidity and the steric hindrance, the presence of a guest inside the cavity, and the guest dimension. Three different quantum mechanical calculation set-ups (in vacuum, with the solvent, and with the solvent and the dispersion correction) were considered. Comparison between theoretical and experimental outcomes suggests that all calculations correctly estimated the most stable isomer, while the inclusion of the dispersion correction is mandatory to reproduce the geometrical parameters. General guidelines can be drawn: less rigid and less bulky is the ligand and less stable is the helicate, and the presence of a guest can strongly affect the isomerism leading to an inversion of the stability by increasing the guest size when the ligand is flexible.

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29

Dang, Li-Long, Tian Chen, Ting-Ting Zhang, Ting-Ting Li, Jun-Liang Song, Ke-Jia Zhang, and Lu-Fang Ma. "Size-Induced Highly Selective Synthesis of Organometallic Rectangular Macrocycles and Heterometallic Cage Based on Half-Sandwich Rhodium Building Block." Molecules 27, no. 12 (June 10, 2022): 3756. http://dx.doi.org/10.3390/molecules27123756.

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The controlled synthesis of organometallic supramolecular macrocycles cages remains interesting and challenging work in the field of supramolecular chemistry. Here, two tetranuclear rectangular macrocycles and an octuclear cage were designed and synthesized utilizing a rigid and functionalized pillar linker, 2,6-bis(pyridin-4-yl)-1,7-dihydrobenzo [1,2-d:4,5-d′]diimidazole (BBI4PY) based on three half-sandwich rhodium building blocks bearing different sizes. X-ray crystallography in combination with 1H NMR spectroscopy elucidated that the two building blocks with shorter spacers only result in rectangular macrocycles. However, the building block of bulkier size to avoid the π-π stacking interactions between two ligands BBI4PY led to the formation of an octuclear cage complex. The latter cage contains two types of metal ions, namely Rh3+ and Cu2+, showing significant characteristics of heterogeneous metal-assembling compounds. In addition, the cage accommodates two free isopropyl ether solvent molecules, thus displaying host–guest behavior.

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Ren, Huimei, Shaozhou Zhu, and Guojun Zheng. "Nanoreactor Design Based on Self-Assembling Protein Nanocages." International Journal of Molecular Sciences 20, no. 3 (January 30, 2019): 592. http://dx.doi.org/10.3390/ijms20030592.

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Self-assembling proteins that form diverse architectures are widely used in material science and nanobiotechnology. One class belongs to protein nanocages, which are compartments with nanosized internal spaces. Because of the precise nanoscale structures, proteinaceous compartments are ideal materials for use as general platforms to create distinct microenvironments within confined cellular environments. This spatial organization strategy brings several advantages including the protection of catalyst cargo, faster turnover rates, and avoiding side reactions. Inspired by diverse molecular machines in nature, bioengineers have developed a variety of self-assembling supramolecular protein cages for use as biosynthetic nanoreactors that mimic natural systems. In this mini-review, we summarize current progress and ongoing efforts creating self-assembling protein based nanoreactors and their use in biocatalysis and synthetic biology. We also highlight the prospects for future research on these versatile nanomaterials.

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31

Fujita, Makoto, and Katsuyuki Ogura. "Supramolecular Self-Assembly of Macrocycles, Catenanes, and Cages through Coordination of Pyridine-Based Ligands to Transition Metals." Bulletin of the Chemical Society of Japan 69, no. 6 (June 1996): 1471–82. http://dx.doi.org/10.1246/bcsj.69.1471.

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32

Zhang, Xing-Xing, Jian Li, and Yun-Yin Niu. "A Review of Crystalline Multibridged Cyclophane Cages: Synthesis, Their Conformational Behavior, and Properties." Molecules 27, no. 20 (October 20, 2022): 7083. http://dx.doi.org/10.3390/molecules27207083.

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This paper reviews the most stable conformation of crystalline three-dimensional cyclophane (CP) achieved by self-assembling based on changing the type of aromatic compound or regulating the type and number of bridging groups. [3n]cyclophanes (CPs) were reported to form supramolecular compounds with bind organic, inorganic anions, or neutral molecules selectively. [3n]cyclophanes ([3n]CPs) have stronger donor capability relative to compound [2n]cyclophanes ([2n]CPs), and it is expected to be a new type of electron donor for the progress of fresh electron conductive materials. The synthesis, conformational behavior, and properties of crystalline multi-bridge rings are summarized and discussed.

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33

Zhang, Zi-En, Yuan-Yuan An, Bo Zheng, Jin-Ping Chang, and Ying-Feng Han. "Hierarchical self-assembly of crown ether based metal-carbene cages into multiple stimuli-responsive cross-linked supramolecular metallogel." Science China Chemistry 64, no. 7 (June 11, 2021): 1177–83. http://dx.doi.org/10.1007/s11426-021-9977-5.

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34

Uhl, Werner, Christina Stefaniak, Matthias Voß, Marcus Layh, Friedhelm Rogel, and Jutta Kösters. "Supramolecular Chemistry Based on Gallium-Gallium Single Bonds - Formation of Large Heterocycles and Cages with up to Twelve Gallium Atoms." Zeitschrift für anorganische und allgemeine Chemie 641, no. 2 (December 4, 2014): 253–60. http://dx.doi.org/10.1002/zaac.201400517.

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35

Shi, Wen‐Jie, Dan Liu, Xin Li, Sha Bai, Yao‐Yu Wang, and Ying‐Feng Han. "Supramolecular Coordination Cages Based on N‐Heterocyclic Carbene‐Gold(I) Ligands and Their Precursors: Self‐Assembly, Structural Transformation and Guest‐Binding Properties." Chemistry – A European Journal 27, no. 29 (April 22, 2021): 7853–61. http://dx.doi.org/10.1002/chem.202100710.

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36

Sumby, Christopher J., Julie Fisher, Timothy J. Prior, and Michaele J. Hardie. "Tris(pyridylmethylamino)cyclotriguaiacylene Cavitands: An Investigation of the Solution and Solid-State Behaviour of Metallo-Supramolecular Cages and Cavitand-Based Coordination Polymers." Chemistry - A European Journal 12, no. 11 (April 3, 2006): 2945–59. http://dx.doi.org/10.1002/chem.200501542.

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Colomban, Cédric, Bastien Châtelet, and Alexandre Martinez. "Different Strategies for Obtaining Enantiopure Hemicryptophanes." Synthesis 51, no. 10 (April 24, 2019): 2081–99. http://dx.doi.org/10.1055/s-0037-1612420.

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Hemicryptophanes have recently emerged as an attractive class of cages due to their interesting applications as supramolecular receptors and catalysts. Over the last decade, substantial advances have been made regarding the preparation of enantiopure versions of these synthetic receptors. Enantiopure hemicryptophanes are commonly obtained through the separation of diastereomers by chromatography, or by resolution of racemic mixtures using chiral HPLC. This short review summarizes the existing methods to access to these chiral organic architectures and discusses the benefits and drawbacks of each approach.1 Introduction2 Enantiopure Hemicryptophanes Obtained by Introducing Additional Chiral Units and Separation of Diastereomers2.1 Synthesis by Means of Intramolecular Macrocyclization Reactions2.2 [1+1] Coupling of the CTV and the Southern Part3 Enantiopure Hemicryptophanes Obtained by Means of Chiral HPLC Resolution of Enantiomers3.1 Resolution of Hemicryptophane Racemates3.2 Resolution of CTV-Based Precursor Racemates4 Conclusion

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Bilyachenko, Alexey N., Ivan S. Arteev, Victor N. Khrustalev, Anna Y. Zueva, Lidia S. Shul’pina, Elena S. Shubina, Nikolay S. Ikonnikov, and Georgiy B. Shul’pin. "Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in The Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity." Molecules 28, no. 3 (January 26, 2023): 1211. http://dx.doi.org/10.3390/molecules28031211.

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A family of unusual octacopper cage methylsilsesquioxanes 1–4 were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages 1–4 due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of Cu8K2-based compound 2) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of Cu8Cs2-based compound 4). Cu8Cs2-complex 4 was evaluated in the catalysis of alkanes and alcohols. Complex 4 exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex 4 as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%.

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Wang, Zhi, Hai-Feng Su, Yuan-Zhi Tan, Stan Schein, Shui-Chao Lin, Wei Liu, Shu-Ao Wang, et al. "Assembly of silver Trigons into a buckyball-like Ag180nanocage." Proceedings of the National Academy of Sciences 114, no. 46 (October 27, 2017): 12132–37. http://dx.doi.org/10.1073/pnas.1711972114.

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Buckminsterfullerene (C60) represents a perfect combination of geometry and molecular structural chemistry. It has inspired many creative ideas for building fullerene-like nanopolyhedra. These include other fullerenes, virus capsids, polyhedra based on DNA, and synthetic polynuclear metal clusters and cages. Indeed, the regular organization of large numbers of metal atoms into one highly complex structure remains one of the foremost challenges in supramolecular chemistry. Here we describe the design, synthesis, and characterization of a Ag180nanocage with 180 Ag atoms as 4-valent vertices (V), 360 edges (E), and 182 faces (F)––sixty 3-gons, ninety 4-gons, twelve 5-gons, and twenty 6-gons––in agreement with Euler’s rule V − E + F = 2. If each 3-gon (or silver Trigon) were replaced with a carbon atom linked by edges along the 4-gons, the result would be like C60, topologically a truncated icosahedron, an Archimedean solid with icosahedral (Ih) point-group symmetry. If C60can be described mathematically as a curling up of a 6.6.6 Platonic tiling, the Ag180cage can be described as a curling up of a 3.4.6.4 Archimedean tiling. High-resolution electrospray ionization mass spectrometry reveals that {Ag3}nsubunits coexist with the Ag180species in the assembly system before the final crystallization of Ag180, suggesting that the silver Trigon is the smallest building block in assembly of the final cage. Thus, we assign the underlying growth mechanism of Ag180to the Silver-Trigon Assembly Road (STAR), an assembly path that might be further employed to fabricate larger, elegant silver cages.

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Astakhov, Grigorii, Mikhail Levitsky, Alexander Korlyukov, Lidia Shul’pina, Elena Shubina, Nikolay Ikonnikov, Anna Vologzhanina, et al. "New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile." Catalysts 9, no. 9 (August 21, 2019): 701. http://dx.doi.org/10.3390/catal9090701.

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Self-assembly of copper(II)phenylsilsesquioxane assisted by the use of 1,10-phenanthroline (phen) results in isolation of two unusual cage-like compounds: (PhSiO1,5)12(CuO)4(NaO0.5)4(phen)4 1 and (PhSiO1,5)6(PhSiO1,5)7(HO0.5)2(CuO)5(O0.25)2(phen)3 2. X-Ray diffraction study revealed extraordinaire molecular architectures of both products. Namely, complex 1 includes single cyclic (PhSiO1,5)12 silsesquioxane ligand. Four sodium ions of 1 are additionally ligated by 1,10-phenanthrolines. In turn, “sodium-less” complex 2 represents coordination of 1,10-phenanthrolines to copper ions. Two silsesquioxane ligands of 2 are: (i) noncondensed cubane of a rare Si6-type and (ii) unprecedented Si7-based ligand including two HOSiO1.5 fragments. These silanol units were formed due to removal of phenyl groups from silicon atoms, observed in mild conditions. The presence of phenanthroline ligands in products 1 and 2 favored the π–π stacking interactions between neighboring cages. Noticeable that in the case of 1 all four phenanthrolines participated in such supramolecular organization, unlike to complex 2 where one of the three phenanthrolines is not “supramolecularly active”. Complexes 1 and 2 were found to be very efficient precatalysts in oxidations with hydroperoxides. A new method for the determination of the participation of hydroxyl radicals has been developed.

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Shi, Wen‐Jie, Dan Liu, Xin Li, Sha Bai, Yao‐Yu Wang, and Ying‐Feng Han. "Cover Feature: Supramolecular Coordination Cages Based on N‐Heterocyclic Carbene‐Gold(I) Ligands and Their Precursors: Self‐Assembly, Structural Transformation and Guest‐Binding Properties (Chem. Eur. J. 29/2021)." Chemistry – A European Journal 27, no. 29 (May 14, 2021): 7811. http://dx.doi.org/10.1002/chem.202101551.

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Yue, Kan, Mingjun Huang, Ryan L. Marson, Jinlin He, Jiahao Huang, Zhe Zhou, Jing Wang, et al. "Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants." Proceedings of the National Academy of Sciences 113, no. 50 (November 28, 2016): 14195–200. http://dx.doi.org/10.1073/pnas.1609422113.

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Frank–Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results from nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation of supramolecular crystals with “soft” spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures.

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Begato, Federico, Roberto Penasa, Giulia Licini, and Cristiano Zonta. "Straight from the bottle! Wine and juice dicarboxylic acids as templates for supramolecular cage self-assembly." Chemical Communications, 2021. http://dx.doi.org/10.1039/d1cc03804d.

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Zhang, Yi-Fan, Ya-Wen Zhang, Xin Li, Li-Ying Sun, and Ying-Feng Han. "Synthesis of Triarylborane-Centered N-Heterocyclic Carbene Cages with Tunable Photophysical Properties." Chemical Communications, 2023. http://dx.doi.org/10.1039/d2cc06584c.

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Triarylborane-based discrete metal-carbene supramolecular cages [M3(1)2](PF6)3 (M = Ag, Au) were synthesized and characterized. The new hexacarbene assemblies show a significant solvatochromic effect in solvents of different polarity. Furthermore, the...

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PooleIII, David, Eduard Bobylev, Simon Mathew, and Joost N. H. Reek. "Entropy directs the self-assembly of supramolecular palladium coordination macrocycles and cages." Chemical Science, 2022. http://dx.doi.org/10.1039/d2sc03154j.

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The self-assembly of palladium-based cages is frequently rationalized via the cumulative enthalpy (ΔH) of bonds between coordination nodes (M, i.e., Pd) and ligand (L) components. This focus on enthalpic rationale...

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Edwardson, Thomas G. W., Stephan Tetter, and Donald Hilvert. "Two-tier supramolecular encapsulation of small molecules in a protein cage." Nature Communications 11, no. 1 (October 26, 2020). http://dx.doi.org/10.1038/s41467-020-19112-1.

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Abstract Expanding protein design to include other molecular building blocks has the potential to increase structural complexity and practical utility. Nature often employs hybrid systems, such as clathrin-coated vesicles, lipid droplets, and lipoproteins, which combine biopolymers and lipids to transport a broader range of cargo molecules. To recapitulate the structure and function of such composite compartments, we devised a supramolecular strategy that enables porous protein cages to encapsulate poorly water-soluble small molecule cargo through templated formation of a hydrophobic surfactant-based core. These lipoprotein-like complexes protect their cargo from sequestration by serum proteins and enhance the cellular uptake of fluorescent probes and cytotoxic drugs. This design concept could be applied to other protein cages, surfactant mixtures, and cargo molecules to generate unique hybrid architectures and functional capabilities.

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Benke, Bahiru Punja, Tobias Kirschbaum, Jürgen Graf, Jürgen H. Gross, and Michael Mastalerz. "Dimeric and trimeric catenation of giant chiral [8 + 12] imine cubes driven by weak supramolecular interactions." Nature Chemistry, December 1, 2022. http://dx.doi.org/10.1038/s41557-022-01094-w.

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AbstractMechanically interlocked structures, such as catenanes and rotaxanes, are fascinating synthetic targets and some are used for molecular switches and machines. Today, the vast majority of catenated structures are built upon macrocycles and only a very few examples of three-dimensional shape-persistent organic cages forming such structures have been reported. However, the catenation in all these cases was based on a thermodynamically favoured π–π-stacking under certain reaction conditions. Here, we show that catenane formation can be induced by adding methoxy or thiomethyl groups to one of the precursors during the synthesis of chiral [8 + 12] imine cubes, giving dimeric and trimeric catenated organic cages. To elucidate the underlying driving forces, we reacted 11 differently 1,4-disubstituted terephthaldehydes with a chiral triamino tribenzotriquinacene under various conditions to study whether monomeric cages or catenated cage dimers are the preferred products. We find that catenation is mainly directed by weak interactions derived from the substituents rather than by π-stacking.

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Liu, Guoliang, Mi Zhou, Kongzhao Su, Ravichandar Babarao, Daqiang Yuan, and Maochun Hong. "Stabilizing the Extrinsic Porosity in Metal–Organic Cages-Based Supramolecular Framework by In Situ Catalytic Polymerization." CCS Chemistry, August 18, 2020, 1382–90. http://dx.doi.org/10.31635/ccschem.020.202000263.

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Li, Kang, Kai Wu, Yan-Zhong Fan, Jing Guo, Yu-Lin Lu, Yuan-Fan Wang, Guillaume Maurin, and Cheng-Yong Su. "Acidic open-cage solution containing basic cage-confined nanospaces for multipurpose catalysis." National Science Review, August 20, 2021. http://dx.doi.org/10.1093/nsr/nwab155.

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Abstract The nanoscale chemical spaces inherent in various organic and metal-organic cages or porous solids and liquids have been continuously explored for their nanoconfinement effect on selective adsorption and reaction of small gas or organic molecules. Herein, we aim to rationalize the unconventional chemical reactivities motivated by the cage-confined nanospaces in aqueous solutions, where the robust yet permeable nanospaces defined by the open-cages facilitate dynamic guest exchange and unusual chemical reactions. The high positive charges on [(Pd/Pt)6(RuL3)8]28+ nanocages drive imidazole-proton equilibrium to display a significantly perturbed pKa shift, creating cage-defined nanospaces in solution with distinct intrinsic basicity and extrinsic acidity. The supramolecular cage effect plays pivotal roles in elaborating robust solution nanospaces, controlling ingress-and-egress molecular processes through open-cage portals, and endowing nanocages with transition-state stabilization, amphoteric reactivities and the phase transfer of insoluble molecules, thus promoting chemical transformations in unconventional ways. Consequently, a wide application of cage-confined catalysis with anomalous reactivities may be expected based on this kind of open-cage solution medium, which combines cage nanocavity, solution heterogeneity and liquid-phase fluidity to benefit various potential mass transfer and molecular process options.

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