A new application for bis(cyclometalated) iridium(III) species containing ancillary acyclic diaminocarbene ligands, viz. for sensing of mercury(II) ions, is disclosed. A family of bis(cyclometalated) iridium(III) species supported by both parent isocyanide and acyclic diaminocarbene ligands was prepared, and their electrochemical and photophysical properties were evaluated, revealing efficient blue-green phosphorescence in solution with quantum yields of up to 55%. We uncovered that the photophysical properties of these complexes are dramatically altered by the presence of metal ions and that the complex [Ir(ppy)(CN){C(NH)(NHCH-4-X)}] with an ADC ligand reacts selectively with Hg ions, enabling its use for sensing of mercury(II) ions in solution. The limit of detection was as low as 2.63 × 10 M, and additional mechanistic studies indicated the formation of an unusual dinuclear iridium(III) cyclometalated intermediate, bridged by a mercury dicyano fragment as a driving force of mercury sensing.
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http://dx.doi.org/10.1021/acs.inorgchem.9b02833 | DOI Listing |
Chemistry
November 2024
LCM, Ecole polytechnique, CNRS, IP Paris, 91128, Palaiseau, France.
Is the J coupling constant for protonated carbene a relevant measure of its σ-donation ability? This paper addresses this question by comparing calculated J values with various experimental and theoretical approaches across a broad spectrum of carbene compounds. We examined Arduengo-type NHCs based on the 2-imidazolylidene scaffold and many other derivatives with modified frameworks, including carbenes with extended, saturated, or conjugated rings, reduced heteroatom stabilization, alternative heteroatoms, permanently charged carbenes, acyclic carbenes, amidocarbenes, and cyclic amino(alkyl/aryl) carbenes, carbodicarbenes and carbodiphosphoranes. Our findings reveal a nuanced relationship between different parameters associated with σ-interaction, such as J, Huynh electronic parameter (HEP), σ-donation from ETS-NOCV, and lone pair energy.
View Article and Find Full Text PDFDalton Trans
September 2024
GIR MIOMET/IU CINQUIMA/Química Inorgánica, Facultad de Ciencias Universidad de Valladolid, 47011, Valladolid, Spain.
A library of new neutral and cationic Ni(II) complexes containing isocyanide ligands and mono- or dialkyl-dithiophosphate have been easily prepared and fully characterized. The synthesis of the neutral complexes unfolds through the alkyl transfer from one alkyldithiophosphate leaving group coordinated to the Ni(II) complex. The alkyl transfer is controlled by steric factors and is highly solvent-dependent.
View Article and Find Full Text PDFChemistry
May 2024
Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034, St. Petersburg, Russian Federation.
Invited for the cover of this issue are Tatiyana Serebryanskaya, Mikhail Kinzhalov and co-workers at St. Petersburg State University, the Research Institute for Physical Chemical Problems, Belarusian State University, Togliatti State University and Blokhin National Medical Research Center of Oncology. The image depicts the shield of Pallas Athena with the structure of a palladium carbene complex that protects against triple-negative breast cancer.
View Article and Find Full Text PDFJ Am Chem Soc
April 2024
Department of Chemistry, University of Houston, 3585 Cullen Blvd. Room 112, Houston, Texas 77204-5003, United States.
Ligand-based functionalization strategies have emerged as powerful approaches to tune and optimize blue phosphorescence, which can involve nucleophilic addition to coordinated ligands or electrophilic functionalization via the coordination of exogenous Lewis acids. Whereas both have been used separately to enhance the photophysical properties of organometallic compounds with high-energy triplet states, in this work, we show that these two strategies can be used together on the same platform. Isocyanide-supported cyclometalated platinum compounds undergo nucleophilic addition with diethylamine to form a strong σ-donor acyclic diaminocarbene-supporting ligand.
View Article and Find Full Text PDFInorg Chem
March 2024
St. Petersburg University, 7-9 Universitetskaya Nab., St. Petersburg 199034, Russian Federation.
Metal-mediated self-assembly of isocyanides and methyl 4-aminopyrimidine-5-carboxylate leads to luminescent Pd and Pt complexes featuring C,N-cyclometalated acyclic diaminocarbene (ADC) ligands. The solid-state luminescent properties of these diaminocarbene derivatives are attributed to their triplet-state metal/metal-to-ligand charge-transfer (MMLCT) nature, which is driven by attractive intermolecular M···M interactions further reinforced by the intramolecular π-π interactions even in the structure of the Pd compound, which is the first Pd-ADC phosphor reported.
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