{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,28]],"date-time":"2026-01-28T12:00:35Z","timestamp":1769601635819,"version":"3.49.0"},"reference-count":43,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2021,6,14]],"date-time":"2021-06-14T00:00:00Z","timestamp":1623628800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["19-73-00300"],"award-info":[{"award-number":["19-73-00300"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100002261","name":"Russian Foundation for Basic Research","doi-asserted-by":"publisher","award":["18-03-00675"],"award-info":[{"award-number":["18-03-00675"]}],"id":[{"id":"10.13039\/501100002261","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100002261","name":"Russian Foundation for Basic Research","doi-asserted-by":"publisher","award":["19-33-60047"],"award-info":[{"award-number":["19-33-60047"]}],"id":[{"id":"10.13039\/501100002261","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C\u2261C bond. Their \u201cclick\u201d 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle \u03c6 of approximately 28\u00b0. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C\u2013H\u2026H\u2013B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C\u2013H\u2026F\u2013B interaction with an adjacent carboranoclathrochelate molecule. The N\u2013H\u2026N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1H-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.<\/jats:p>","DOI":"10.3390\/molecules26123635","type":"journal-article","created":{"date-parts":[[2021,6,14]],"date-time":"2021-06-14T22:25:46Z","timestamp":1623709546000},"page":"3635","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents\u2014The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C\u2261C Bond(s)"],"prefix":"10.3390","volume":"26","author":[{"given":"Genrikh E.","family":"Zelinskii","sequence":"first","affiliation":[{"name":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninskii pr., 31, 119991 Moscow, Russia"},{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ilya P.","family":"Limarev","sequence":"additional","affiliation":[{"name":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninskii pr., 31, 119991 Moscow, Russia"},{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6228-303X","authenticated-orcid":false,"given":"Anna V.","family":"Vologzhanina","sequence":"additional","affiliation":[{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0199-5172","authenticated-orcid":false,"given":"Valentina A.","family":"Olshevskaya","sequence":"additional","affiliation":[{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Anton V.","family":"Makarenkov","sequence":"additional","affiliation":[{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Pavel V.","family":"Dorovatovskii","sequence":"additional","affiliation":[{"name":"National Research Center Kurchatov Institute, 1 Kurchatova pl., 123098 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alexander S.","family":"Chuprin","sequence":"additional","affiliation":[{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mikhail A.","family":"Vershinin","sequence":"additional","affiliation":[{"name":"Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the Russian Academy of Sciences, 3 Lavrentieva prosp., 630090 Novosibirsk, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3858-6097","authenticated-orcid":false,"given":"Semyon V.","family":"Dudkin","sequence":"additional","affiliation":[{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2823-6560","authenticated-orcid":false,"given":"Yan Z.","family":"Voloshin","sequence":"additional","affiliation":[{"name":"Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninskii pr., 31, 119991 Moscow, Russia"},{"name":"Nesmeyanov Institute of the Organoelement Compounds of the Russian Academy of Sciences, Vavilova Str., 28, 119991 Moscow, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,6,14]]},"reference":[{"key":"ref_1","unstructured":"Voloshin, Y.Z., Kostromina, N.A., and Kr\u00e4mer, R. 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