Low symmetry and functionalised organic cages prepared using Eglinton and Sonogashira coupling reactions

References

• Yang X, Ullah Z, Stoddart JF, et al. Porous organic cages. Chem Rev. 2023;123(8):4602–4634. doi: 10.1021/acs.chemrev.2c00667
   PubMed Web of Science ®Google Scholar
• Yoshizawa M, Klosterman JK, Fujita M. Functional molecular flasks: new properties and reactions within discrete, self-assembled hosts. Angew Chem Int Ed. 2009;48(19):3418–3438. doi: 10.1002/anie.200805340
   PubMed Web of Science ®Google Scholar
• Cook TR, Stang PJ. Recent developments in the preparation and chemistry of Metallacycles and metallacages via coordination. Chem Rev. 2015;115(15):7001–7045. doi: 10.1021/cr5005666
   PubMed Web of Science ®Google Scholar
• Hasell T, Cooper AI. Porous organic cages: soluble, modular and molecular pores. Nat Rev Mater. 2016;1(9):16053. doi: 10.1038/natrevmats.2016.53
   Web of Science ®Google Scholar
• Sudik AC, Millward AR, Ockwig NW, et al. Design, synthesis, structure, and gas (N 2, ar, CO 2, CH 4, and H 2) sorption properties of porous metal-organic tetrahedral and Heterocuboidal Polyhedra. J Am Chem Soc. 2005;127(19):7110–7118. doi: 10.1021/ja042802q
   PubMed Web of Science ®Google Scholar
• Tozawa T, Jones JTA, Swamy SI, et al. Porous organic cages. Nat Mater. 2009;8(12):973. doi: 10.1038/nmat2545
   PubMed Web of Science ®Google Scholar
• Zhang G, Presly O, White F, et al. A permanent mesoporous organic cage with an exceptionally high surface area. Angew Chem Int Ed. 2014;53(6):1516–1520. doi: 10.1002/anie.201308924
   PubMed Web of Science ®Google Scholar
• Jones JTA, Hasell T, Wu X, et al. Modular and predictable assembly of porous organic molecular crystals. Nature. 2011;474(7351):367–371. doi: 10.1038/nature10125
   PubMed Web of Science ®Google Scholar
• Evans JD, Huang DM, Hill MR, et al. Molecular design of amorphous porous organic cages for enhanced gas storage. J Phys Chem C. 2015;119(14):7746–7754. doi: 10.1021/jp512944r
   Web of Science ®Google Scholar
• Taggart GA, Antonio AM, Lorzing GR, et al. Tuning the porosity, solubility, and gas-storage properties of cuboctahedral coordination cages via Amide or Ester Functionalization. ACS Appl Mater Interfaces. 2020;12(22):24913–24919. doi: 10.1021/acsami.0c06434
   PubMed Web of Science ®Google Scholar
• Gosselin AJ, Decker GE, Antonio AM, et al. A charged coordination cage-based porous salt. J Am Chem Soc. 2020;142(21):9594–9598. doi: 10.1021/jacs.0c02806
   PubMed Web of Science ®Google Scholar
• Smulders MMJ, Riddell IA, Browne C, et al. Building on architectural principles for three-dimensional metallosupramolecular construction. Chem Soc Rev. 2013;42(4):1728–1754. doi: 10.1039/C2CS35254K
   PubMed Web of Science ®Google Scholar
• Liu X, Liu Y, Li G, et al. One-pot, 18-component synthesis of an octahedral nanocontainer molecule. Angew Chem Int Ed. 2006;45(6):901–904. doi: 10.1002/anie.200504049
   PubMed Web of Science ®Google Scholar
• Francesconi O, Ienco A, Moneti G, et al. A self-assembled pyrrolic cage receptor specifically recognizes β-Glucopyranosides. Angew Chem Int Ed. 2006;45(40):6693–6696. doi: 10.1002/anie.200602412
   PubMed Web of Science ®Google Scholar
• Skowronek P, Gawronski J. Chiral iminospherand of a tetrahedral symmetry spontaneously assembled in a [6 + 4] cyclocondensation. Org Lett. 2008;10(21):4755–4758. doi: 10.1021/ol801702j
   PubMed Web of Science ®Google Scholar
• Nishimura N, Kobayashi K. Self-assembly of a cavitand-based capsule by dynamic boronic ester formation. Angew Chem Int Ed. 2008;47(33):6255–6258. doi: 10.1002/anie.200802293
   PubMed Web of Science ®Google Scholar
• Christinat N, Scopelliti R, Severin K. Multicomponent assembly of boronic acid based macrocycles and cages. Angew Chem Int Ed. 2008;47(10):1848–1852. doi: 10.1002/anie.200705272
   PubMed Web of Science ®Google Scholar
• Mastalerz M, Schneider MW, Oppel IM, et al. A salicylbisimine cage compound with high surface area and selective CO 2 /CH 4 adsorption. Angew Chem Int Ed. 2011;50(5):1046–1051. doi: 10.1002/anie.201005301
   PubMed Web of Science ®Google Scholar
• Zhang G, Mastalerz M. Organic cage compounds – from shape-persistency to function. Chem Soc Rev. 2014;43(6):1934–1947. doi: 10.1039/C3CS60358J
   PubMed Web of Science ®Google Scholar
• We note that recent advances in alkyne metathesis chemistry and hydrazone chemistry may offer a method to prepare robust cages under thermodynamic control, although the ability to form low symmetry species using these approaches is still limited. See e.g. Lee S, Yang A, Moneypenny TP II, et al. Kinetically trapped tetrahedral cages via Alkyne Metathesis. J Am Chem Soc. 2016;138(7):2182–2185. doi: 10.1021/jacs.6b00468 and Jiao T, Wu G, Zhang Y, et al. Self-assembly in water with N-substituted imines. Angew Chem Int Ed. 2020;59(42):18350-18367. doi: 10.1002/anie.201910739
   PubMed Web of Science ®Google Scholar
• Schneider MW, Oppel IM, Griffin A, et al. Post-modification of the interior of porous shape-persistent organic cage compounds. Angew Chem Int Ed. 2013;52(13):3611–3615. doi: 10.1002/anie.201208156
   PubMed Web of Science ®Google Scholar
• Bhat AS, Elbert SM, Zhang W-S, et al. Transformation of a [4+6] salicylbisimine cage to chemically robust amide cages. Angew Chem Int Ed. 2019;58(26):8819–8823. doi: 10.1002/anie.201903631
   PubMed Web of Science ®Google Scholar
• Alexandre P-E, Zhang W-S, Rominger F, et al. A robust porous quinoline cage: transformation of a [4+6] salicylimine cage by Povarov Cyclization. Angew Chem Int Ed. 2020;59(44):19675–19679. doi: 10.1002/anie.202007048
   PubMed Web of Science ®Google Scholar
• Andrews KG, Christensen KE. Access to amide-linked organic cages by in situ trapping of Metastable Imine Assemblies: solution phase bisamine recognition. Chem: Eur J. 2023;29(26):e202300063. doi: 10.1002/chem.202300063
   PubMed Web of Science ®Google Scholar
• Bloch WM, Clever GH. Integrative self-sorting of coordination cages based on ‘naked’ metal ions. Chem Commun. 2017;53(61):8506–8516. doi: 10.1039/C7CC03379F
   PubMed Web of Science ®Google Scholar
• Lewis JEM, Tarzia A, White AJP, et al. Conformational control of Pd 2 L 4 assemblies with unsymmetrical ligands. Chem Sci. 2020;11(3):677–683. doi: 10.1039/C9SC05534G
   Web of Science ®Google Scholar
• Tian C-B, Sun Q-F. Combinatorial coordination self-assembly for organopalladium cages with fine-tuned structure and function. Chem: Eur J. 2023;29(28):e202300195. doi: 10.1002/chem.202300195
   PubMed Web of Science ®Google Scholar
• Wu K, Benchimol E, Baksi A, et al. ChemRxiv. doi:10.26434/chemrxiv-2023-5gb4g.
   Google Scholar
• Preston D, Evans JD. A lantern-shaped Pd(II) cage constructed from four different low-symmetry ligands with positional and orientational control: an ancillary pairings approach. Chem Int Ed. 2023;62(49):e202314378. doi: 10.1002/anie.202314378
   PubMed Web of Science ®Google Scholar
• Zhang C, Chen C-F. Synthesis and structure of a Triptycene-based nanosized molecular cage. J Org Chem. 2007;72(24):9339–9341. doi: 10.1021/jo7017526
   PubMed Web of Science ®Google Scholar
• Avellaneda A, Valente P, Burgun A, et al. Kinetically controlled porosity in a robust organic cage material. Angew Chem Int Ed. 2013;52(13):3746–3749. doi: 10.1002/anie.201209922
   PubMed Web of Science ®Google Scholar
• Kitchin M, Konstas K, Sumby CJ, et al. Continuous flow synthesis of a carbon-based molecular cage macrocycle via a three-fold homocoupling reaction. Chem Commun. 2015;51(75):14231–14234. doi: 10.1039/C5CC05181A
   PubMed Web of Science ®Google Scholar
• Burgun A, Valente P, Evans JD, et al. Endohedrally functionalised porous organic cages. Chem Commun. 2016;52(57):8850–8853. doi: 10.1039/C6CC04423A
   PubMed Web of Science ®Google Scholar
• Tominaga M, Ohara K, Yamaguchi K, et al. Hollow sphere formation from a three-dimensional structure composed of an Adamantane-Based Cage. J Org Chem. 2014;79(14):6738–6742. doi: 10.1021/jo500989c
   PubMed Web of Science ®Google Scholar
• Ma H, Zhai T-L, Wang Z, et al. Switching porosity of stable triptycene-based cage via solution-state assembly processes. RSC Adv. 2020;10(15):9088–9092. doi: 10.1039/D0RA00128G
   PubMed Web of Science ®Google Scholar
• Zhang Z-Q, Ren Q-X, Tian W-F, et al. Synthesis of enantiopure hydrocarbon cages based on an optically resolved C 3 -symmetric triaminotribenzotriquinacene. Org Lett. 2021;23(4):1478–1483. doi: 10.1021/acs.orglett.1c00176
   PubMed Web of Science ®Google Scholar
• Thomas CM, Liang W, Preston D, et al. Post-synthetic modification of a porous hydrocarbon cage to give a Discrete Co 24 organometallic Complex. Chem: Eur J. 2022;28(51):e202200958. doi: 10.1002/chem.202200958
   PubMed Web of Science ®Google Scholar
• We note that generally the term Eglinton coupling is used to refer to the Cu(II)-mediated coupling of two terminal alkynes to give a di-alkyne and that our reactions, which are based on those developed by Sumby and Doonan use both a Cu(I) and Cu(II) mediator (reference 31). Other copper-mediated coupling reactions were also investigated (see Supporting Information). In the interests of simplicity, we refer to these reactions as Eglinton reactions throughout.
   Google Scholar
• Hoskins BF, Robson R. Infinite polymeric frameworks consisting of three dimensionally linked rod-like segments. J Am Chem Soc. 1989;111(15):5962–5964. doi: 10.1021/ja00197a079
   Web of Science ®Google Scholar
• Robson R. Design and its limitations in the construction of bi- and poly-nuclear coordination complexes and coordination polymers (aka MOFs): a personal view. Dalton Trans. 2008;38:5113–5131. doi: 10.1039/b805617j
   PubMed Web of Science ®Google Scholar
• Yaghi OM, O’Keeffe M, Ockwig NW, et al. Reticular synthesis and the design of new materials. Nature. 2003;423(6941):705–714. doi: 10.1038/nature01650
   PubMed Web of Science ®Google Scholar
• Morshedi M, Thomas M, Tarzia A, et al. Supramolecular anion recognition in water: synthesis of hydrogen-bonded supramolecular frameworks. Chem Sci. 2017;8(4):3019–3025. doi: 10.1039/C7SC00201G
   PubMed Web of Science ®Google Scholar
• Xing G, Yan T, Das S, et al. Synthesis of crystalline porous organic salts with high proton conductivity. Angew Chem Int Ed. 2018;57(19):5345–5349. doi: 10.1002/anie.201800423
   PubMed Web of Science ®Google Scholar
• Bassanetti I, Bracco S, Comotti A, et al. Flexible porous molecular materials responsive to CO 2 , CH 4 and Xe stimuli. J Mater Chem A. 2018;6(29):14231–14239. doi: 10.1039/C8TA02211A
   Web of Science ®Google Scholar
• White NG. Amidinium⋯carboxylate frameworks: predictable, robust, water-stable hydrogen bonded materials. Chem Commun. 2021;57(84):10998–11008. doi: 10.1039/D1CC04782E
   PubMed Web of Science ®Google Scholar
• Spek AL. PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. Acta Crystallogr. 2015;C71:9–8.
   Google Scholar
• Bruno IJ, Cole JC, Edgington PR, et al. New software for searching the Cambridge structural database and visualizing crystal structures. Acta Crystallogr. 2002;B58(3):389–397. doi: 10.1107/S0108768102003324
   Google Scholar
• Boer SA, Morshedi M, Tarzia A, et al. Molecular tectonics: a node-and-linker building block approach to a family of hydrogen-bonded frameworks. Chem: Eur J. 2019;25(42):10006–10012. doi: 10.1002/chem.201902117
   PubMed Web of Science ®Google Scholar
• Kwon Y-D, Son J, Chun J-H. Catalyst-Free Aromatic Radiofluorination via Oxidized Iodoarene Precursors. Org Lett. 2018;20(24):7902–7906. doi: 10.1021/acs.orglett.8b03450
   PubMed Web of Science ®Google Scholar
• Alagille D, DaCosta H, Chen Y, et al. Potent mGlur5 antagonists: pyridyl and thiazolyl-ethynyl-3,5-disubstituted-phenyl series. Bioorg Med Chem Lett. 2011;21(11):3243–3247. doi: 10.1016/j.bmcl.2011.04.047
   PubMed Web of Science ®Google Scholar
• Endres A, Maas G. Dirhodium(II) tetrakis(perfluoroalkylbenzoates) as partially recyclable catalysts for carbene transfer reactions with diazoacetates. Tetrahedron. 2002;58(20):3999–4005. doi: 10.1016/S0040-4020(02)00249-1
   Web of Science ®Google Scholar
• Aragao D, Aishima J, Cherukuvada H, et al. MX2: a high-flux undulator microfocus beamline serving both the chemical and macromolecular crystallography communities at the Australian synchrotron. J Synchrotron Rad. 2018;25(3):885–891. doi: 10.1107/S1600577518003120
   PubMedGoogle Scholar
• Kabsch W. XDS. Acta Crystallogr. 2010;66(2):125–132. doi: 10.1107/S0907444909047337
   PubMedGoogle Scholar
• Palatinus L, Chapuis G. SUPERFLIP – a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J Appl Crystallogr. 2007;40(4):786–790. doi: 10.1107/S0021889807029238
   Web of Science ®Google Scholar
• Betteridge PW, Carruthers JR, Cooper RI, et al. CRYSTALS version 12: software for guided crystal structure analysis. J Appl Crystallogr. 2003;36(6):1487. doi: 10.1107/S0021889803021800
   Google Scholar