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One‐Pot Intercalation Strategy for the Encapsulation of a CO‐Releasing Organometallic Molecule in a Layered Double Hydroxide
Author(s) -
Calhau Isabel B.,
Gomes Ana C.,
Bruno Sofia M.,
Coelho Ana C.,
Magalhães Clara I. R.,
Romão Carlos C.,
Valente Anabela A.,
Gonçalves Isabel S.,
Pillinger Martyn
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000202
Subject(s) - chemistry , coprecipitation , intercalation (chemistry) , hydroxide , molecule , decarbonylation , crystallography , layered double hydroxides , nuclear chemistry , inorganic chemistry , organic chemistry , catalysis
The photoactivatable CO‐releasing molecule (photoCORM) [Mo(CO) 3 (CNCH 2 COOH) 3 ] (ALF795) has been incorporated into a Zn,Al layered double hydroxide (LDH) host by a coprecipitation synthesis strategy. Powder X‐ray diffraction (PXRD) of the resultant material Zn,Al‐ALF795 showed that the ALF795 guest molecules assembled into a monolayer to give a basal spacing of 16.0 Å. FTIR and 13 C{ 1 H} CP MAS NMR spectroscopy confirmed that the molecular structure of the tricarbonyl complex was retained upon intercalation. Scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDS) and elemental analyses confirmed the phase‐purity of Zn,Al‐ALF795. The myoglobin assay was used to demonstrate that intercalated ALF795 retains the photoactive behavior of the free CORM, with a substantial fraction (42 %) of the high CO payload (2.46 mmol g –1 ) being released after exposure to UV light for 3 h under simulated physiological conditions. In addition, gas chromatography was used to track sequential light‐ and H 2 O 2 ‐triggered decarbonylation of free and intercalated ALF795. In biological buffer solution (HEPES), less than 2 % Mo leaching from Zn,Al‐ALF795 took place after 5 h, showing the strong capacity of the LDH host to retain the unaltered complex and decarbonylation fragments.