title: Luminescent Re(I) Carbonyl Complexes as Trackable PhotoCORMs for CO delivery to Cellular Targets.
abstract: A family of Re(I) carbonyl complexes of general formula [ReX(CO)3(phen)]0/1+(where X = Cl-, CF3SO3-, MeCN, PPh3, and methylimidazole) derived from 1,10-phenanthroline (phen) exhibits variable emission characteristics depending on the presence of the sixth ancillary ligand/group (X). All complexes but with X = MeCN exhibit moderate CO release upon irradiation with low-power UV light and are indefinitely stable in anaerobic/aerobic environment in solution as well as in solid state when kept under dark condition. These CO donors liberate three, one, or no CO depending on the nature of sixth ligand upon illumination as studied with the aid of time-dependent IR spectroscopy. Results of excited-state density functional theory (DFT) and time-dependent DFT calculations provided insight into the origin of the emission characteristics of these complexes. The luminescent rheinum(I) photoCORMs uniformly displayed efficient cellular internalization by the human breast adenocarcinoma cells, MDA-MB-231, while the complex with PPh3as ancillary ligand showed moderate nuclear localization in addition to the cytosolic distribution. These species hold significant promise as theranostic photoCORMs (photoinduced CO releasing molecules), where the entry of the pro-drug can be tracked within the cellular matrices.
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Santa Cruz, California 95064, United States.
authors.forename: Indranil
authors.initials: I
authors.lastname: Chakraborty
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Santa Cruz, California 95064, United States.
authors.forename: Jorge
authors.initials: J
authors.lastname: Jimenez
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , Sapporo 060-0810, Japan.
authors.forename: W M C
authors.identifier: http://orcid.org/0000-0003-0213-0688
authors.initials: WM
authors.lastname: Sameera
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University , Sapporo 060-0810, Japan.
authors.forename: Masako
authors.initials: M
authors.lastname: Kato
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Santa Cruz, California 95064, United States.
authors.forename: Pradip K
authors.identifier: http://orcid.org/0000-0002-7044-944X
authors.initials: PK
authors.lastname: Mascharak
mesh_terms: D001943:Breast Neoplasms / Q000000981:diagnostic imaging*; D002248:Carbon Monoxide / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004337:Drug Carriers / Q000737:chemistry; D016503:Drug Delivery Systems; D005260:Female; D006801:Humans; D049449:Luminescence; D008163:Luminescent Measurements; D008958:Models, Molecular; D015394:Molecular Structure; D055668:Photochemical Processes; D011789:Quantum Theory; D012211:Rhenium / Q000737:chemistry*; D013997:Time Factors; D014407:Tumor Cells, Cultured
chemical_list: D056831:Coordination Complexes; D004337:Drug Carriers; D012211:Rhenium; D002248:Carbon Monoxide