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Five rod\u2010shaped di\u2010pyridyl Fe<jats:sup>II<\/jats:sup>\u2010metalloligands, with varied length (1.5 \u2013 3.2\u00a0nm), lateral substituents, and number of iron centers, were used to bridge two Ru<jats:sup>II<\/jats:sup>\u2010metallacycles, made of two coplanar Zn<jats:sup>II<\/jats:sup>\u2010porphyrin each. The resulting architectures consist of four Ru<jats:sup>II<\/jats:sup> complexes, four zinc\u2010porphyrins, and either two or four Fe<jats:sup>II<\/jats:sup>\u2010clathrochelate units. Earlier, geometrically similar <jats:italic>sandwich\u2010like<\/jats:italic> architectures were based on purely organic connectors. Among other novel characteristics, the use of metalloligands was found to be beneficial for the overall stability, thus allowing for a solution\u2010based characterization of the assemblies. Single crystal X\u2010ray structures were determined for the complete collection, highlighting additional key features: the two facing Zn<jats:sup>II<\/jats:sup>\u2010porphyrin platforms are set wide apart according to the span of the two connecting metalloligands, while the latter are parallelly aligned by the anchoring Zn<jats:sup>II<\/jats:sup>\u2010porphyrin\/Ru<jats:sup>II<\/jats:sup>\u2010metallacycles, at fixed inter Fe\u00b7\u00b7Fe distance(s). Mutual control over these geometrical parameters is very strict, as evidenced by self\u2010sorting experiments. Useful implementation of these systems into functional systems may be envisaged by pairing the peripheral metalloporphyrin photosensitizers with photo\/redox\/catalytically active inner metal cores.<\/jats:p>","DOI":"10.1002\/chem.202501811","type":"journal-article","created":{"date-parts":[[2025,7,3]],"date-time":"2025-07-03T07:04:17Z","timestamp":1751526257000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Discrete Heterotrimetallic Assemblies Based on Rod\u2010Shaped Fe<sup>II<\/sup>\u2010Metalloligands and a Zn<sup>II<\/sup>\u2010Porphyrin\/Ru<sup>II<\/sup>\u2010Metallacycle"],"prefix":"10.1002","volume":"31","author":[{"given":"Agnese","family":"Amati","sequence":"first","affiliation":[{"name":"Department of Chemical and Pharmaceutical Sciences University of Trieste  Via L. Giorgieri 1 Trieste 34127 Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giacomo","family":"Cecot","sequence":"additional","affiliation":[{"name":"Institut des Sciences et Ing\u00e9nierie Chimiques \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL)  Lausanne 1015 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9102-3053","authenticated-orcid":false,"given":"Irene","family":"Regeni","sequence":"additional","affiliation":[{"name":"Department of Chemical and Pharmaceutical Sciences University of Trieste  Via L. Giorgieri 1 Trieste 34127 Italy"},{"name":"Institut de Science et d'Ing\u00e9nierie Supramol\u00e9culaires University of Strasbourg  8 all\u00e9e Gaspard Monge, BP 70028 Strasbourg F\u201067083 Cedex France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7655-4585","authenticated-orcid":false,"given":"Erica","family":"Giraldi","sequence":"additional","affiliation":[{"name":"Department of Chemical and Pharmaceutical Sciences University of Trieste  Via L. Giorgieri 1 Trieste 34127 Italy"},{"name":"Institut des Sciences et Ing\u00e9nierie Chimiques \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL)  Lausanne 1015 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2224-7234","authenticated-orcid":false,"given":"Kay","family":"Severin","sequence":"additional","affiliation":[{"name":"Institut des Sciences et Ing\u00e9nierie Chimiques \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL)  Lausanne 1015 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0288-3233","authenticated-orcid":false,"given":"Nicola","family":"Demitri","sequence":"additional","affiliation":[{"name":"Elettra\u2013Synchrotron Light Source  S.S. 14 Km 163.5 in Area Science Park, 34149 Basovizza Trieste Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0115-6560","authenticated-orcid":false,"given":"Elisabetta","family":"Iengo","sequence":"additional","affiliation":[{"name":"Department of Chemical and Pharmaceutical Sciences University of Trieste  Via L. 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Still it is quite clear that ligand basicity is the dominant factor over effective molarities contributions for the overall stability of multivalent assemblies.[59\u201362]"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00063D"},{"key":"e_1_2_8_60_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201004201"},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902490"},{"key":"e_1_2_8_62_1","first-page":"77","volume-title":"Advances in Physical Organic Chemistry","author":"Motloch P.","year":"2018"},{"key":"e_1_2_8_63_1","unstructured":"During this study single crystals suitable for X\u2010ray analysis of two model compounds 2aTPP2 2cTPP2 have also been isolated. Both structures that can be formulated as {Zn\u00b7TPP}2{4\u2032\u2010dipyridyl\u2010FeII(clathrochelate)}2 consist of two facing ZnII\u2010meso\u2010tetraphenylporphyrin connected by either2aor2c(see Figures S3 S37 S40 and Tables S2 S3)."},{"key":"e_1_2_8_64_1","unstructured":"CCDC 2388760\u20132388767 contain the supplementary crystallographic data for compounds2aTPP2 2cTPP2 5a 5a\u2019 5b 5c 6 and7. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viahttps:\/\/www.ccdc.cam.ac.uk\/structures."},{"key":"e_1_2_8_65_1","unstructured":"ESI\u2010MS analysis was not helpful asmix1suffers from the same drawbacks highlighted for5a\u2010c 6and7(see also mass analysis discussion and Figure S31 in the SI).[53]"},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1140\/epjp\/i2015-15043-3"},{"key":"e_1_2_8_67_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0907444909047337"},{"key":"e_1_2_8_68_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0907444910045749"},{"key":"e_1_2_8_69_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0907444913000061"},{"key":"e_1_2_8_70_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2053229614024218"},{"key":"e_1_2_8_71_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0907444910007493"},{"key":"e_1_2_8_72_1","doi-asserted-by":"publisher","DOI":"10.1107\/S090744490804362X"},{"key":"e_1_2_8_73_1","unstructured":"Diamond \u2010 Crystal and Molecular Structure Visualization Crystal Impact \u2010 K. 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