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To alter the interactions between HDACs and half-sandwich organometallic HDACis, we introduced amphiphilic 1,3,5-triaza-7-phosphaadamantane (PTA) or lipophilic triphenylphosphine (PPh3) as coligands. The half-sandwich compounds were found to be stable in aqueous solution, and the Rh(III) derivatives exhibited promising antiproliferative and HDAC inhibitory activity compared to their chlorido precursor. The lipophilic Rh\u2013PPh3 compound was effectively taken up into human cancer cells, where it caused \u03b1-tubulin hyperacetylation with low impact on the histone H3 acetylation level. Molecular docking studies revealed additional interactions on the surface of the protein due to the presence of the P-donor ligands. Coordination of a CoIII(cyclen) chaperone to the hydroxamic acid moiety yielded reduction-responsive heterobimetallic compounds in which the bioactivity of the hydroxamic acid moiety was effectively masked.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c02897","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T14:35:43Z","timestamp":1785854143000},"page":"18969-18984","source":"Crossref","is-referenced-by-count":0,"title":["Tuning HDAC\nInhibition, Cell Uptake, and Antiproliferative\nActivity of Vorinostat-Derived Half-Sandwich Complexes with Phosphine\nCo-Ligands"],"prefix":"10.1021","volume":"65","author":[{"given":"Chen","family":"Chen","sequence":"first","affiliation":[{"name":"University of Auckland, Private Bag 92019 , , ,","place":["Auckland, New Zealand, 1010"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Barbora","family":"Havli\u0301nova\u0301","sequence":"additional","affiliation":[{"name":"Institute of Biotechnology of the Czech Academy of Sciences , ,","place":["Vestec, Czech Republic, 252 50"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miroslava","family":"Vos\u030cahli\u0301kova\u0301","sequence":"additional","affiliation":[{"name":"Institute of Biotechnology of the Czech Academy of Sciences , ,","place":["Vestec, Czech Republic, 252 50"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ru\u030az\u030cena","family":"Tuc\u030ckova\u0301","sequence":"additional","affiliation":[{"name":"Institute of Biotechnology of the Czech Academy of Sciences , ,","place":["Vestec, Czech Republic, 252 50"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zexiong","family":"Lin","sequence":"additional","affiliation":[{"name":"University of Auckland, Private Bag 92019 , , ,","place":["Auckland, New Zealand, 1010"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2751-3060","authenticated-orcid":true,"given":"Cyril","family":"Bar\u030cinka","sequence":"additional","affiliation":[{"name":"Institute of Biotechnology of the Czech Academy of Sciences , ,","place":["Vestec, Czech Republic, 252 50"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5485-9211","authenticated-orcid":true,"given":"Stephen M. 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