The synthesis and physical-chemical characterization of the metal-ligand complex [Os(bpy)2(CO)(enIA)][OTf]2 (where enIA = ethylenediamine iodoacetamide) with a sulfhydryl-specific functional group is described. The UV and visible absorption and luminescence emission, including lifetime and steady-state anisotropy, are reported for the free probe and the probe covalently linked to two test proteins. The spectroscopic properties of the probe are unaffected by chemical modification and subsequent covalent linkage to the proteins. The luminescence lifetime in aqueous buffer is approximately 200 ns and the limiting anisotropy is greater than 0.125, suggesting a potentially useful probe for biophysical investigations.
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http://dx.doi.org/10.1021/ic048452q | DOI Listing |
Inorg Chem
January 2025
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Herein, we investigate the effects of ligand design on the nuclearity and reactivity of metal-ligand multiply bonded (MLMB) complexes to access an exclusively bimetallic reaction pathway for C-H bond functionalization. To this end, the diiron alkoxide [Fe(Dbf)] () was treated with 3,5-bis(trifluoromethyl)phenyl azide to access the diiron imido complex [Fe(Dbf)(μ-NCHF)] () that promotes hydrogen atom abstraction (HAA) from a variety of C-H and O-H bond containing substrates. A diiron bis(amide) complex [Fe(Dbf)(μ-NHCHF)(NHCHF)] () was generated, prompting the isolation of the analogous bridging amide terminal alkoxide [Fe(Dbf)(μ-NHCHF)(OCH)] () and the asymmetric pyridine-bound diiron imido [Fe(Dbf)(μ-NCHF)(NCH)] ().
View Article and Find Full Text PDFSmall
January 2025
Department of Chemistry, Gwangju Institute of Science and Technology (GIST), Gwangju, 61005, Republic of Korea.
Extreme ultraviolet (EUV) lithography has enabled significant reductions in device dimensions but is often limited by capillary force-driven pattern collapse in conventional wet processes. Recent dry-development approaches, while promising, frequently require toxic etchants or specialized equipment, limiting their broader applicability and highlighting the need for more sustainable, cost-effective alternatives. In this study, highly reactive, etchant-free dry-developable EUV photoresists using N-heterocyclic carbene (NHC)-based metal-ligand complexes, achieving half-saturation at EUV doses of 8.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260, United States.
ConspectusUnderstanding f element-ligand covalency is at the center of efforts to design new separations schemes for spent nuclear fuel, and is therefore of signficant fundamental and practical importance. Considerable effort has been invested into quantifying covalency in f element-ligand bonding. Over the past decade, numerous studies have employed a variety of techniques to study covalency, including XANES, EPR, and optical spectroscopies, as well as X-ray crystallography.
View Article and Find Full Text PDFDalton Trans
January 2025
Department of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060, Nishikawatsu, Matsue, Shimane, 690-8504, Japan.
Paddlewheel-type diruthenium(II,II) complexes are paramagnetic with two unpaired electrons ( = 1) and can be utilized as versatile building blocks for higher-order structures, such as supramolecular complexes, coordination polymers, and metal-organic frameworks, although they are generally highly air-sensitive. In this study, we developed an air-stable paddlewheel-type diruthenium(II,II) complex with two electron-withdrawing 1,8-naphthyridine-2-carboxylate (npc) ligands, [Ru(μ-npc)(OCMe)] (1). The two acetate ligands in 1 can be replaced by other carboxylate ligands; the solvothermal reactions of 1 with benzoic acid (HOCPh) yields the heteroleptic [Ru(μ-npc)(OCPh)] (2), whereas its reaction with 1,8-naphthyridine-2-carboxylic acid (Hnpc) produces the homoleptic [Ru(μ-npc)(η-npc)] (3).
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China.
A thorium-carbon double bond that corresponds to the sum of theoretical covalent double bond radii has long been sought after in the study of actinide-ligand multiple bonding as a synthetic target. However, the stabilization of this chemical bond remains a great challenge to date, in part because of a relatively poor energetic matching between 5f-/6d- orbitals of thorium and the 2s-/2p- frontier orbitals of carbon. Herein, we report the successful synthesis of a thorium-carbon double bond in a carbon-bridged actinide-transition metal cluster, i.
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