{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,10]],"date-time":"2026-03-10T22:46:52Z","timestamp":1773182812965,"version":"3.50.1"},"reference-count":40,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2021,2,2]],"date-time":"2021-02-02T00:00:00Z","timestamp":1612224000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Three new heterometallic [CrIII8NiII6] coordination cubes of formulae [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7(H2O)5](ClO4)12 (2), and [CrIII8NiII6L24Cl12] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrIIIL3] and the corresponding NiII salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight CrIII and six NiII ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on (1) reveal weak ferromagnetic interactions between the CrIII and NiII ions, with JCr-Ni = + 0.045 cm\u22121. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the CrIII ions. Excluding wheel-like structures, examples of large heterometallic clusters containing both CrIII and NiII ions are rather rare, and we demonstrate that the use of metalloligands with predictable bonding modes allows for a modular approach to building families of related polymetallic complexes. Compounds (1)\u2013(3) join the previously published, structurally related family of [MIII8MII6] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd.<\/jats:p>","DOI":"10.3390\/molecules26030757","type":"journal-article","created":{"date-parts":[[2021,2,2]],"date-time":"2021-02-02T05:44:42Z","timestamp":1612244682000},"page":"757","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["[CrIII8NiII6]n+ Heterometallic Coordination Cubes"],"prefix":"10.3390","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0044-2469","authenticated-orcid":false,"given":"Helen M.","family":"O\u2019Connor","sequence":"first","affiliation":[{"name":"EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH3 5JF, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4790-4184","authenticated-orcid":false,"given":"Sergio","family":"Sanz","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH3 5JF, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8692-3815","authenticated-orcid":false,"given":"Aaron J.","family":"Scott","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH3 5JF, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mateusz B.","family":"Pitak","sequence":"additional","affiliation":[{"name":"UK National Crystallography Service, Chemistry, Highfield Campus, University of Southampton, Southampton SO17 1BJ, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wim T.","family":"Klooster","sequence":"additional","affiliation":[{"name":"UK National Crystallography Service, Chemistry, Highfield Campus, University of Southampton, Southampton SO17 1BJ, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8414-9272","authenticated-orcid":false,"given":"Simon J.","family":"Coles","sequence":"additional","affiliation":[{"name":"UK National Crystallography Service, Chemistry, Highfield Campus, University of Southampton, Southampton SO17 1BJ, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nicholas F.","family":"Chilton","sequence":"additional","affiliation":[{"name":"Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Eric J. L.","family":"McInnes","sequence":"additional","affiliation":[{"name":"Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Paul J.","family":"Lusby","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH3 5JF, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"H\u00f8gni","family":"Weihe","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Stergios","family":"Piligkos","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9365-370X","authenticated-orcid":false,"given":"Euan K.","family":"Brechin","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry, The University of Edinburgh, David Brewster Road, Edinburgh EH3 5JF, UK"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,2,2]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"6942","DOI":"10.1021\/ja902570u","article-title":"Nickel\u2212Iron Dithiolato Hydrides Relevant to the [NiFe]-Hydrogenase Active Site","volume":"131","author":"Barton","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"5876","DOI":"10.1039\/c001675f","article-title":"A structural and functional mimic of the active site of NiFe hydrogenases","volume":"46","author":"Canaguier","year":"2010","journal-title":"Chem. Commun."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"28","DOI":"10.1021\/cr500208k","article-title":"Multimetallic Catalysis Based on Heterometallic Complexes and Clusters","volume":"115","author":"Buchwalter","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1938","DOI":"10.1021\/acsenergylett.9b00874","article-title":"Heterometallic Metal\u2013Organic Frameworks (MOFs): The Advent of Improving the Energy Landscape","volume":"4","author":"Rice","year":"2019","journal-title":"ACS Energy Lett."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1016\/j.ccr.2016.09.010","article-title":"Recent advances in the construction and applications of heterometallic macrocycles and cages","volume":"344","author":"Zhang","year":"2017","journal-title":"Coord. Chem. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1871","DOI":"10.1016\/j.ccr.2007.10.030","article-title":"Advances in acyclic compartmental ligands and related complexes","volume":"252","author":"Vigato","year":"2008","journal-title":"Coord. Chem. Rev."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"701","DOI":"10.1038\/378701a0","article-title":"A room-temperature organometallic magnet based on Prussian blue","volume":"378","author":"Ferlay","year":"1995","journal-title":"Nature"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"11627","DOI":"10.1021\/ic4019794","article-title":"Two-Dimensional Coordination Polymers Constructed by [NiIILnIII] Nodes and [WIV(bpy)(CN)6]2\u2212 Spacers: A Network of [NiIIDyIII] Single Molecule Magnets","volume":"52","author":"Alexandru","year":"2013","journal-title":"Inorg. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"8636","DOI":"10.1021\/ic2011875","article-title":"Syntheses, Structures, and Magnetic Properties of Low-Dimensional Heterometallic Complexes Based on the Versatile Building Block [(Tp)Cr(CN)3]\u2212","volume":"50","author":"Yao","year":"2011","journal-title":"Inorg. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"10058","DOI":"10.1021\/ic061347r","article-title":"Structural and Magnetic Studies on Cyano-Bridged Rectangular Fe2M2 (M. = Cu, Ni) Clusters","volume":"45","author":"Liu","year":"2006","journal-title":"Inorg. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"325","DOI":"10.1021\/ar040158e","article-title":"Directed Assembly of Metal\u2212Cyanide Cluster Magnets","volume":"38","author":"Beltran","year":"2005","journal-title":"Acc. Chem. Res."},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Rebilly, J.N., and Mallah, T. (2006). Synthesis of Single-Molecule Magnets Using Metallocyanates. Single-Mol. Magn. Relat. Phenom., 103\u2013131.","DOI":"10.1007\/430_032"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"4672","DOI":"10.1039\/b926030g","article-title":"Recipes for enhanced molecular cooling","volume":"39","author":"Evangelisti","year":"2010","journal-title":"Dalton Trans."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4677","DOI":"10.1039\/b925358k","article-title":"Effects of frustration on magnetic molecules: A survey from Olivier Kahn until today","volume":"39","author":"Schnack","year":"2010","journal-title":"Dalton Trans."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Milios, C.J., and Winpenny, R.E.P. (2015). Cluster-Based Single-Molecule Magnets. Mol. Nanomagnets Relat. Phenom., 1\u2013109.","DOI":"10.1007\/430_2014_149"},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Coulon, C., Pianet, V., Urdampilleta, M., and Cl\u00e9rac, R. (2015). Single-Chain Magnets and Related Systems. Mol. Nanomagnets Relat. Phenom., 143\u2013184.","DOI":"10.1007\/430_2014_154"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"301","DOI":"10.1038\/s41557-019-0232-y","article-title":"Molecular spins for quantum computation","volume":"11","author":"Luis","year":"2019","journal-title":"Nat. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"105","DOI":"10.1002\/ange.200390002","article-title":"Synthesis and Characterization of Heterometallic {Cr7M} Wheels","volume":"115","author":"Larsen","year":"2003","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"14543","DOI":"10.1038\/ncomms14543","article-title":"Portraying entanglement between molecular qubits with four-dimensional inelastic neutron scattering","volume":"8","author":"Garlatti","year":"2017","journal-title":"Nat. Commun."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"9681","DOI":"10.1002\/anie.200803637","article-title":"Heterometallic Rings Made From Chromium Stick Together Easily","volume":"47","author":"Timco","year":"2008","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Timco, G.A., Batsanov, A.S., Larsen, F.K., Muryn, C.A., Overgaard, J., Teat, S.J., and Winpenny, R.E.P. (2005). Influencing the nuclearity and constitution of heterometallic rings via templates. Chem. Commun., 3649\u20133651.","DOI":"10.1039\/b504912a"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"11834","DOI":"10.1039\/C8DT00685G","article-title":"Order in disorder: Solution and solid-state studies of [MIII2MII5] wheels (MIII = Cr, Al; MII = Ni, Zn)","volume":"47","author":"Fraser","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"58","DOI":"10.1039\/C7DT04043A","article-title":"Constructing CrIII-centered heterometallic complexes: [NiII6CrIII] and [CoII6CrIII] wheels","volume":"47","author":"Kakaroni","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_24","first-page":"231","article-title":"Synthesis and crystalline-structure of pentanuclear heterometallic pivaltoacetylacetonate complexes","volume":"20","author":"Manole","year":"1994","journal-title":"Koord. Khim."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"6132","DOI":"10.1002\/anie.200461006","article-title":"Templating Open- and Closed-Chain Structures around Metal Complexes of Macrocycles","volume":"43","author":"Heath","year":"2004","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"6761","DOI":"10.1002\/anie.201501041","article-title":"[CrIII8MII6]12+Coordination Cubes (MII=Cu, Co)","volume":"54","author":"Sanz","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3500","DOI":"10.1021\/acs.inorgchem.7b02674","article-title":"Modular [FeIII8MII6]n+ (MII = Pd, Co, Ni, Cu) Coordination Cages","volume":"57","author":"Sanz","year":"2018","journal-title":"Inorg. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"4914","DOI":"10.1039\/C6CE00654J","article-title":"[CrIII8MII6]n+ (MII = Cu, Co) face-centred, metallosupramolecular cubes","volume":"18","author":"Sanz","year":"2016","journal-title":"CrystEngComm"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"5526","DOI":"10.1039\/C7SC00487G","article-title":"[MIII2MII3]n+ trigonal bipyramidal cages based on diamagnetic and paramagnetic metalloligands","volume":"8","author":"Sanz","year":"2017","journal-title":"Chem. Sci."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"6810","DOI":"10.1021\/cr200077m","article-title":"Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles","volume":"111","author":"Chakrabarty","year":"2011","journal-title":"Chem. Rev."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"7343","DOI":"10.1002\/anie.200903575","article-title":"Construction of Heterometallic Cages with Tripodal Metalloligands","volume":"48","author":"Wu","year":"2009","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"4858","DOI":"10.1021\/jm00104a012","article-title":"Novel cAMP PDE III inhibitors: 1,6-naphthyridin-2(1H)-ones","volume":"35","author":"Singh","year":"1992","journal-title":"J. Med. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"683","DOI":"10.1039\/C2SC00955B","article-title":"Changing and challenging times for service crystallography","volume":"3","author":"Coles","year":"2011","journal-title":"Chem. Sci."},{"key":"ref_34","unstructured":"Rigaku, O., CrysAlis, P.R.O., and Rigaku Oxford Diffraction (2021, January 18). CrysAlisPro. Available online: https:\/\/www.rigaku.com\/zh-hans\/products\/smc\/crysalis."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"615","DOI":"10.1107\/S0021889893002018","article-title":"Crystal handling at low temperatures","volume":"26","author":"Kottke","year":"1993","journal-title":"J. Appl. Crystallogr."},{"key":"ref_36","first-page":"3","article-title":"SHELXT\u2014Integrated space-group and crystal-structure determination","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Cryst."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1283","DOI":"10.1107\/S0021889803015267","article-title":"OLEX: New software for visualization and analysis of extended crystal structures","volume":"36","author":"Dolomanov","year":"2003","journal-title":"J. Appl. Crystallogr."},{"key":"ref_38","unstructured":"Wong, S.S.M. (1986). Nuclear Statistical Spectroscopy, Clarendon Press."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"275","DOI":"10.1139\/v95-037","article-title":"Antiferromagnetism and metamagnetism in 1,4-diazine and pyridine complexes of nickel(II)","volume":"73","author":"Otieno","year":"1995","journal-title":"Can. J. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2308","DOI":"10.1016\/j.ccr.2006.03.016","article-title":"Multi-frequency, high-field EPR as a powerful tool to accurately determine zero-field splitting in high-spin transition metal coordination complexes","volume":"250","author":"Krzystek","year":"2006","journal-title":"Coord. Chem. Rev."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/3\/757\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T05:18:36Z","timestamp":1760159916000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/3\/757"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,2,2]]},"references-count":40,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2021,2]]}},"alternative-id":["molecules26030757"],"URL":"https:\/\/doi.org\/10.3390\/molecules26030757","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.13636586.v1","asserted-by":"object"}]},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,2,2]]}}}