Please use this identifier to cite or link to this item: http://hdl.handle.net/10773/42483
Title: Host-guest complexes of cucurbit[8]uril and [(η5-C5H4R)Mo(CO)3CH3] (R = H, CO2CH3) for controlled release of carbon monoxide
Author: Gomes, Ana C.
Monteiro, Rodrigo P.
Calhau, Isabel B.
Lopes, André D.
Gonçalves, Isabel S.
Pillinger, Martyn
Keywords: CO-releasing molecules
Molybdenum
Encapsulation
Cucurbituril
Myoglobin assay
Issue Date: 1-Oct-2024
Publisher: Elsevier
Abstract: The monosubstituted cyclopentadienyl half-sandwich molybdenum(II) tricarbonyl complex [(η5 -C5H4CO2CH3) Mo(CO)3CH3] (1) and its 1:1 inclusion compound with cucurbit[8]uril (1@CB8) have been prepared and characterised by elemental and thermogravimetric analyses, powder X-ray diffraction, diffuse reflectance UV–vis, solid-state 13C{1 H} MAS NMR, FT-IR, and Raman spectroscopies. The CO-releasing behaviours of 1, 1@CB8 and, for comparison, [(η5 -C5H5)Mo(CO)3CH3] (2) and its 1:1 inclusion complex with CB8, were assessed using a deoxymyoglobin-carbonmonoxymyglobin assay. For assays performed in the dark at 37 ◦C, complex 1 undergoes thermally assisted spontaneous CO release, with ca. 0.5 equivalents of CO being released after 6 h. The half-life (t1/2) of 325 min identifies 1 as a slow releaser when compared to complex 2 bearing the unsubstituted cyclopentadienyl ligand (t1/2 = 25 min). CO release from 1 was promoted by exposure to UV light (t1/2 = 85 min), establishing the complex as a photochemically activated CO-releasing molecule (photoCORM). For 1@CB8, t1/2 for photo-assisted CO release increased to ca. 7 h, and for 2@CB8 the dark-release t1/2 increased to 165 min, showing that molecular acceptors like cucurbiturils can be used effectively as second-sphere ligands to modulate the CO release profile of CORMs.
Peer review: yes
URI: http://hdl.handle.net/10773/42483
DOI: 10.1016/j.jorganchem.2024.123312
ISSN: 0022-328X
Publisher Version: https://www.sciencedirect.com/science/article/pii/S0022328X24003073?via%3Dihub
Appears in Collections:CICECO - Artigos
DQ - Artigos

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