{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T14:12:26Z","timestamp":1785161546005,"version":"3.55.0"},"reference-count":54,"publisher":"American Chemical Society (ACS)","issue":"7","license":[{"start":{"date-parts":[[2026,7,15]],"date-time":"2026-07-15T00:00:00Z","timestamp":1784073600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100018694","name":"HORIZON EUROPE Marie Sklodowska-Curie Actions","doi-asserted-by":"publisher","award":["101208969"],"award-info":[{"award-number":["101208969"]}],"id":[{"id":"10.13039\/100018694","id-type":"DOI","asserted-by":"publisher"}]},{"name":"German Research Council (DFG)","award":["445470598"],"award-info":[{"award-number":["445470598"]}]},{"name":"German Research Council (DFG)","award":["445471097"],"award-info":[{"award-number":["445471097"]}]},{"name":"German Research Council (DFG)","award":["564094473"],"award-info":[{"award-number":["564094473"]}]},{"name":"German Research Council (DFG)","award":["INST 40\/575-1 FUGG"],"award-info":[{"award-number":["INST 40\/575-1 FUGG"]}]},{"name":"Horizon 2020 European Commission (EC)","award":["101088146"],"award-info":[{"award-number":["101088146"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,7,27]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Antiaromatic compounds are often difficult to work with due to their relative instability in comparison with aromatic analogues. As a consequence, their application in functional materials remains in its infancy. Here, we report the synthesis of porous MII4L6 (M = Fe, Zn) coordination cages equipped with dibenzo[a,e]pentalene panels involving the antiaromatic motif of pentalene stabilized by benzannulation. Both cages encapsulate fullerene C60, with the more adaptable zinc(II) cage also binding C70, undergoing pronounced structural reconfiguration upon C60 inclusion, and displaying broader affinity for polycyclic aromatic hydrocarbons. The cages selectively bind anthraquinone over its reduced form and interact with steroids such as testosterone and cholesterol. Remarkably, the chemical shifts of the guests are affected by the aromatic Clar sextets rather than the antiaromatic pentalene motif. These assemblies represent only the second reported example of a supramolecular cage with a cavity fully enclosed by antiaromatic walls and demonstrate that benzannulated antiaromatic motifs can be incorporated into cages without interrupting conventional host\u2013guest behavior, while simultaneously allowing for a systematic tuning of magnetic shielding effects.<\/jats:p>","DOI":"10.1021\/jacsau.6c00720","type":"journal-article","created":{"date-parts":[[2026,7,16]],"date-time":"2026-07-16T02:25:37Z","timestamp":1784168737000},"page":"4221-4229","source":"Crossref","is-referenced-by-count":0,"title":["Tetrahedral\n                    <i>M<\/i>\n                    II4L6 (\n                    <i>M<\/i>\n                    = Fe, Zn) Cages Equipped with Walls\nFeaturing Antiaromatic Pentalene Motifs"],"prefix":"10.1021","volume":"6","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3799-0485","authenticated-orcid":true,"given":"Wojciech","family":"Stawski","sequence":"first","affiliation":[{"name":"Ulm University , , Albert-Einstein-Allee 11 , ,","place":["Ulm, Germany, 89081"]},{"name":"Ulm University , , Lise-Meitner Str. 16 , ,","place":["Ulm, Germany, 89081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2430-1380","authenticated-orcid":true,"given":"Birgit","family":"Esser","sequence":"additional","affiliation":[{"name":"Ulm University , , Albert-Einstein-Allee 11 , ,","place":["Ulm, Germany, 89081"]},{"name":"Ulm University , , Lise-Meitner Str. 16 , ,","place":["Ulm, Germany, 89081"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,15]]},"reference":[{"key":"2026072709072417400_cit1","doi-asserted-by":"publisher","first-page":"4383","DOI":"10.1021\/ja00993a023","article-title":"Antiaromaticity of Cyclopropenyl\nAnions","volume":"89","author":"Breslow","year":"1967","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit2","doi-asserted-by":"publisher","first-page":"393","DOI":"10.1021\/ar50072a001","article-title":"Antiaromaticity","volume":"6","author":"Breslow","year":"1973","journal-title":"Acc. Chem. Res."},{"key":"2026072709072417400_cit3","doi-asserted-by":"publisher","first-page":"18677","DOI":"10.1039\/D4SC05318D","article-title":"Antiaromaticity\nin Molecular Assemblies and Materials","volume":"15","author":"Lavendomme","year":"2024","journal-title":"Chem.\nSci."},{"key":"2026072709072417400_cit4","doi-asserted-by":"publisher","first-page":"4811","DOI":"10.1021\/ja00973a009","article-title":"Induced Paramagnetic\nRing Currents","volume":"88","author":"Pople","year":"1966","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit5","doi-asserted-by":"publisher","first-page":"15984","DOI":"10.1038\/ncomms15984","article-title":"Highly-Conducting Molecular\nCircuits Based on Antiaromaticity","volume":"8","author":"Fujii","year":"2017","journal-title":"Nat. Commun."},{"key":"2026072709072417400_cit6","doi-asserted-by":"publisher","first-page":"745","DOI":"10.1039\/D0CC06810A","article-title":"Single-Molecule\nConductance of Dibenzopentalenes: Antiaromaticity and Quantum Interference","volume":"57","author":"Schmidt","year":"2021","journal-title":"Chem. Commun."},{"key":"2026072709072417400_cit7","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202400935","article-title":"Low-Lying\nLUMO Boosts\nConductance in Antiaromatic Dibenzopentalene Versus Aromatic Analogues","volume":"30","author":"Schmidt","year":"2024","journal-title":"Chem. - Eur. J."},{"key":"2026072709072417400_cit8","doi-asserted-by":"publisher","first-page":"249","DOI":"10.1021\/ja01056a030","article-title":"The Pentalenyl Dianion","volume":"86","author":"Katz","year":"1964","journal-title":"J. Am.\nChem. Soc."},{"key":"2026072709072417400_cit9","doi-asserted-by":"publisher","first-page":"904","DOI":"10.1039\/J29710000904","article-title":"Annulenes.\nPart XII. The Dianion\nof [12]Annulene","volume":"0","author":"Oth","year":"1971","journal-title":"J. Chem. Soc. B"},{"key":"2026072709072417400_cit10","doi-asserted-by":"publisher","first-page":"3498","DOI":"10.1021\/ja00765a042","article-title":"Radical Anion\nand the Dianion of [16] Annulene","volume":"94","author":"Oth","year":"1972","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026072709072417400_cit11","doi-asserted-by":"publisher","first-page":"603","DOI":"10.1021\/cr00064a006","article-title":"Reduction\nand Oxidation of Annulenes","volume":"84","author":"Mu\u0308llen","year":"1984","journal-title":"Chem. Rev."},{"key":"2026072709072417400_cit12","doi-asserted-by":"publisher","first-page":"7514","DOI":"10.1021\/ja00336a035","article-title":"Diatropic Cyclophane Dianions","volume":"106","author":"Mu\u0308llen","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit13","doi-asserted-by":"publisher","first-page":"4964","DOI":"10.1002\/chem.202005131","article-title":"Cations and Anions of Dibenzo[a,e]Pentalene\nand Reduction of a Dibenzo[a,e]Pentalenophane","volume":"27","author":"Hermann","year":"2021","journal-title":"Chem. - Eur. J."},{"key":"2026072709072417400_cit14","doi-asserted-by":"publisher","first-page":"14109","DOI":"10.1039\/d3sc04251k","article-title":"Crystallographic\nEvidence for Global Aromaticity in the Di-Anion and Tetra-Anion of\na Cyclophane Hydrocarbon","volume":"14","author":"Stawski","year":"2023","journal-title":"Chem. Sci."},{"key":"2026072709072417400_cit15","doi-asserted-by":"publisher","first-page":"998","DOI":"10.1038\/s41557-024-01469-1","article-title":"The Anti-Aromatic Dianion and Aromatic Tetraanion of\n[18]Annulene","volume":"16","author":"Stawski","year":"2024","journal-title":"Nat. Chem."},{"key":"2026072709072417400_cit16","doi-asserted-by":"publisher","first-page":"977","DOI":"10.1021\/acs.accounts.7b00004","article-title":"Explorations of\nthe Indenofluorenes\nand Expanded Quinoidal Analogues","volume":"50","author":"Frederickson","year":"2017","journal-title":"Acc. Chem.\nRes."},{"key":"2026072709072417400_cit17","doi-asserted-by":"publisher","first-page":"1541","DOI":"10.1038\/s41557-023-01341-8","article-title":"Tetrafluorenofulvalene\nas a Sterically\nFrustrated Open-Shell Alkene","volume":"15","author":"Prajapati","year":"2023","journal-title":"Nat. Chem."},{"key":"2026072709072417400_cit18","doi-asserted-by":"publisher","first-page":"1869","DOI":"10.1021\/ja963439t","article-title":"Pentalene: Formation,\nElectronic, and Vibrational Structure","volume":"119","author":"Bally","year":"1997","journal-title":"J. Am.\nChem. Soc."},{"key":"2026072709072417400_cit19","doi-asserted-by":"publisher","first-page":"575","DOI":"10.1002\/anie.197305751","article-title":"1,3,5-Tri-Tert-Butylpentalene.\nA Stabilized Planar\n8\u03c0-Electron System","volume":"12","author":"Hafner","year":"1973","journal-title":"Angew. Chem., Int.\nEd. Engl."},{"key":"2026072709072417400_cit20","doi-asserted-by":"publisher","first-page":"300","DOI":"10.1246\/cl.2010.300","article-title":"Pentaleno[1,2-c:4,5-C\u2032]Dithiophene\nDerivatives: First Synthesis, Properties, and a Molecular Structure","volume":"39","author":"Konishi","year":"2010","journal-title":"Chem. Lett."},{"key":"2026072709072417400_cit21","doi-asserted-by":"publisher","first-page":"1520","DOI":"10.1021\/ol200213h","article-title":"Synthesis\nof a Pentalene Centered Polycyclic Fused System","volume":"13","author":"Yin","year":"2011","journal-title":"Org. Lett."},{"key":"2026072709072417400_cit22","doi-asserted-by":"publisher","first-page":"965","DOI":"10.1039\/c3sc52623b","article-title":"Pentalenes\nwith Novel Topologies: Exploiting the Cascade Carbopalladation Reaction\nbetween Alkynes and Gem-Dibromoolefins","volume":"5","author":"London","year":"2014","journal-title":"Chem.\nSci."},{"key":"2026072709072417400_cit23","doi-asserted-by":"publisher","first-page":"4924","DOI":"10.1021\/ol502440d","article-title":"Diaceno[a,e]Pentalenes from Homoannulations\nof o-Alkynylaryliodides\nUtilizing a Unique Pd(OAc)2\/n-Bu4NOAc Catalytic Combination","volume":"16","author":"Shen","year":"2014","journal-title":"Org. Lett."},{"key":"2026072709072417400_cit24","doi-asserted-by":"publisher","first-page":"3071","DOI":"10.1002\/cber.19120450334","article-title":"U\u0308ber\ngefa\u0308rbte Kohlenwasserstoffe der Diphensuccinden-Reihe. I","volume":"45","author":"Brand","year":"1912","journal-title":"Ber. Dtsch. Chem. Ges."},{"key":"2026072709072417400_cit25","doi-asserted-by":"publisher","first-page":"3035","DOI":"10.1039\/D4OB00114A","article-title":"Identification and Quantification of Local Antiaromaticity in Polycyclic\nAromatic Hydrocarbons (PAHs) Based on the Magnetic Criterion","volume":"22","author":"Kleinpeter","year":"2024","journal-title":"Org. Biomol. Chem."},{"key":"2026072709072417400_cit26","doi-asserted-by":"publisher","first-page":"700","DOI":"10.1016\/j.tet.2017.12.020","article-title":"Paramagnetic\nRing Current Effects in Anti-Aromatic Structures Subject\nto Substitution\/Annelation Quantified by Spatial Magnetic Properties\n(TSNMRS)","volume":"74","author":"Kleinpeter","year":"2018","journal-title":"Tetrahedron"},{"key":"2026072709072417400_cit27","doi-asserted-by":"publisher","first-page":"34","DOI":"10.1021\/acs.joc.9b01195","article-title":"Synthesis and Properties\nof Conjugated\nNanohoops Incorporating Dibenzo[a,e]Pentalenes: [2]DBP[12]CPPs","volume":"85","author":"Wassy","year":"2020","journal-title":"J. Org. Chem."},{"key":"2026072709072417400_cit28","doi-asserted-by":"publisher","first-page":"10775","DOI":"10.1002\/anie.202016968","article-title":"Chiral Dibenzopentalene-Based\nConjugated\nNanohoops through Stereoselective Synthesis","volume":"133","author":"Hermann","year":"2021","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026072709072417400_cit29","doi-asserted-by":"publisher","first-page":"12244","DOI":"10.1021\/jacs.1c05251","article-title":"[N]Cyclodibenzopentalenes\nas Antiaromatic Curved Nanocarbons with High Strain and Strong Fullerene\nBinding","volume":"143","author":"Wo\u0308ssner","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit30","doi-asserted-by":"publisher","first-page":"737","DOI":"10.1055\/a-1740-7139","article-title":"Conjugated Nanohoops with Dibenzo[a,e]pentalenes\nas Nonalternant and Antiaromatic \u03c0-Systems","volume":"33","author":"Esser","year":"2022","journal-title":"Synlett"},{"key":"2026072709072417400_cit31","doi-asserted-by":"publisher","first-page":"e202306184","DOI":"10.1002\/anie.202306184","article-title":"Conjugated\nNanohoop Polymers Based\non Antiaromatic Dibenzopentalenes for Charge Storage in Organic Batteries","volume":"62","author":"Seitz","year":"2023","journal-title":"Angew. Chem. Int. Ed."},{"key":"2026072709072417400_cit32","doi-asserted-by":"publisher","first-page":"983","DOI":"10.1021\/acs.orglett.1c03900","article-title":"Increased Antiaromaticity\nthrough Pentalene Connection in [n]Cyclo-1,5-dibenzopentalenes","volume":"24","author":"Wo\u0308ssner","year":"2022","journal-title":"Org. Lett."},{"key":"2026072709072417400_cit33","doi-asserted-by":"publisher","first-page":"2840","DOI":"10.1021\/jacs.2c10501","article-title":"Antiaromatic Covalent Organic Frameworks\nBased on Dibenzopentalenes","volume":"145","author":"Sprachmann","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit34","doi-asserted-by":"publisher","first-page":"9","DOI":"10.1039\/c4cs00222a","article-title":"Metal\u2013organic\nmolecular cages: applications of biochemical implications","volume":"44","author":"Ahmad","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"2026072709072417400_cit35","doi-asserted-by":"publisher","first-page":"2600","DOI":"10.1021\/acs.accounts.0c00434","article-title":"Molecular\nPhotoswitching in Confined\nSpaces","volume":"53","author":"Grommet","year":"2020","journal-title":"Acc. Chem. Res."},{"key":"2026072709072417400_cit36","doi-asserted-by":"publisher","first-page":"405","DOI":"10.1038\/s41557-022-01103-y","article-title":"Enantioselective fullerene functionalization\nthrough stereochemical information transfer from a self-assembled\ncage","volume":"15","author":"Lu","year":"2023","journal-title":"Nat. Chem."},{"key":"2026072709072417400_cit37","doi-asserted-by":"publisher","first-page":"5186","DOI":"10.1021\/jacs.3c10808","article-title":"Regioswitchable\nBingel\nBis-Functionalization of Fullerene C70 via Supramolecular\nMasks","volume":"146","author":"Iannace","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit38","doi-asserted-by":"publisher","first-page":"511","DOI":"10.1038\/s41586-019-1661-x","article-title":"An Antiaromatic-Walled Nanospace","volume":"574","author":"Yamashina","year":"2019","journal-title":"Nature"},{"key":"2026072709072417400_cit39","doi-asserted-by":"publisher","first-page":"e202420989","DOI":"10.1002\/anie.202420989","article-title":"Intramolecular\nCharge Transfer in\nAntiaromatic Donor\/Acceptor-Fused s-Indacenes","volume":"137","author":"Demachkie","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"2026072709072417400_cit40","doi-asserted-by":"publisher","first-page":"2879","DOI":"10.1016\/s0957-4166(03)00543-3","article-title":"Enantioselective Radical\nReactions: The Use of Metal\nTriflimides as Lewis Acids","volume":"14","author":"Sibi","year":"2003","journal-title":"Tetrahedron Asymmetry"},{"key":"2026072709072417400_cit41","doi-asserted-by":"publisher","first-page":"13652","DOI":"10.1021\/ja205254s","article-title":"Controlling the\nTransmission of Stereochemical Information through Space in Terphenyl-Edged\nFe4L6 Cages","volume":"133","author":"Meng","year":"2011","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026072709072417400_cit42","doi-asserted-by":"publisher","first-page":"1050","DOI":"10.1039\/C7SC04070A","article-title":"Binding of Anions in Triply Interlocked\nCoordination Catenanes and\nDynamic Allostery for Dehalogenation Reactions","volume":"9","author":"Yang","year":"2018","journal-title":"Chem. Sci."},{"key":"2026072709072417400_cit43","doi-asserted-by":"publisher","first-page":"2006","DOI":"10.1039\/c8sc05085f","article-title":"Waterproof\nArchitectures through Subcomponent Self-Assembly","volume":"10","author":"Perca\u0301stegui","year":"2019","journal-title":"Chem. Sci."},{"key":"2026072709072417400_cit44","doi-asserted-by":"publisher","first-page":"5101","DOI":"10.1039\/d0cs00801j","article-title":"Transformation Networks\nof Metal\u2013Organic Cages Controlled by Chemical Stimuli","volume":"51","author":"Benchimol","year":"2022","journal-title":"Chem. Soc. Rev."},{"key":"2026072709072417400_cit45","doi-asserted-by":"publisher","first-page":"1033","DOI":"10.1107\/S1600576722004988","article-title":"MoloVol: An\nEasy-to-Use Program for Analyzing Cavities,\nVolumes and Surface Areas of Chemical Structures","volume":"55","author":"Maglic","year":"2022","journal-title":"J. Appl. Crystallogr."},{"key":"2026072709072417400_cit46","doi-asserted-by":"publisher","first-page":"5557","DOI":"10.1038\/ncomms6557","article-title":"Sponge-like Molecular Cage for Purification of Fullerenes","volume":"5","author":"Garci\u0301a-Simo\u0301n","year":"2014","journal-title":"Nat. Commun."},{"key":"2026072709072417400_cit47","doi-asserted-by":"publisher","first-page":"40","DOI":"10.1039\/C5CS00315F","article-title":"Metallosupramolecular Receptors for\nFullerene Binding and Release","volume":"45","author":"Garci\u0301a-Simo\u0301n","year":"2016","journal-title":"Chem. Soc. Rev."},{"key":"2026072709072417400_cit48","doi-asserted-by":"publisher","first-page":"11008","DOI":"10.1021\/jacs.7b05788","article-title":"Tuning the Redox\nProperties of Fullerene Clusters within a Metal\u2013Organic Capsule","volume":"139","author":"Rizzuto","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit49","doi-asserted-by":"publisher","first-page":"13","DOI":"10.1021\/je900296s","article-title":"Solubility of Light Fullerenes in Organic Solvents","volume":"55","author":"Semenov","year":"2010","journal-title":"J. Chem. Eng. Data"},{"key":"2026072709072417400_cit50","doi-asserted-by":"publisher","first-page":"9698","DOI":"10.1021\/jacs.7b05202","article-title":"Design\nPrinciples for the Optimization\nof Guest Binding in Aromatic-Paneled FeII4L6 Cages","volume":"139","author":"Ronson","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit51","doi-asserted-by":"publisher","first-page":"15615","DOI":"10.1021\/ja507617h","article-title":"Pyrene-Edged\nFeII4L6 Cages Adaptively Reconfigure\nDuring Guest Binding","volume":"136","author":"Ronson","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"2026072709072417400_cit52","doi-asserted-by":"publisher","first-page":"2685","DOI":"10.1002\/cbic.201900072","article-title":"RNA Dynamics by NMR Spectroscopy","volume":"20","author":"Marus\u030cic\u030c","year":"2019","journal-title":"ChemBioChem"},{"key":"2026072709072417400_cit53","doi-asserted-by":"publisher","first-page":"1549","DOI":"10.1016\/j.chempr.2023.03.011","article-title":"Enantiopure\nFeII4L4 Cages Bind Steroids Stereoselectively","volume":"9","author":"Li","year":"2023","journal-title":"Chem"},{"key":"2026072709072417400_cit54","doi-asserted-by":"publisher","first-page":"7374","DOI":"10.1002\/chem.201800322","article-title":"Dibenzo[a,e]Pentalenophanes: Bending\na Non-Alternant Hydrocarbon","volume":"24","author":"Hermann","year":"2018","journal-title":"Chem. - Eur. J."}],"container-title":["JACS Au"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacsau.6c00720","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jaaucr\/article-pdf\/6\/7\/4221\/65968022\/jacsau.6c00720.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jaaucr\/article-pdf\/6\/7\/4221\/65968022\/jacsau.6c00720.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T13:24:11Z","timestamp":1785158651000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jaaucr\/article\/6\/7\/4221\/5211390\/Tetrahedral-MII4L6-M-Fe-Zn-Cages-Equipped-with"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,15]]},"references-count":54,"journal-issue":{"issue":"7","published-online":{"date-parts":[[2026,7,15]]},"published-print":{"date-parts":[[2026,7,27]]}},"URL":"https:\/\/doi.org\/10.1021\/jacsau.6c00720","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.15003016\/v2","asserted-by":"object"}]},"ISSN":["2691-3704"],"issn-type":[{"value":"2691-3704","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,15]]}}}