Surface ligands significantly influence the optical properties and stability of metal nanoclusters. In this study, we synthesized [Pt1Ag31(S-Adm)16(DPPM)3(DPPMO)Cl3](SbF6)4 (Pt1Ag31-DPPMO). Compared to [Pt1Ag31(S-Adm)16(DPPM)3Cl3](SbF6)4 (Pt1Ag31), the introduction of secondary phosphine oxide ligand, DPPMO, results in Pt1Ag31-DPPMO exhibiting enhanced photoluminescent properties in both solution and solid states, as well as improved stability and electron-withdrawing ability. This work presents a novel strategy to regulate the properties of metal nanoclusters, especially enhancing photoluminescence performance and stability, through the incorporation of secondary phosphine oxide ligand.
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Crystal structures of six complexes of phosphane chalcogenides P ( = -butyl or isopropyl, = S or Se) with the metal halides ( = Pd or Pt, = Cl or Br), two halochalcogenyl-phospho-nium derivatives ( Bu PrPBr)[PdBr] and one hydrolysis product.
Acta Crystallogr E Crystallogr Commun
March 2025
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany.
The complexes - (: = BuPrPSe, = Pd, = Cl; : = Bu PrPSe, = Pd, = Cl; : = Bu PrPSe, = Pd, = Br; : = Bu PrPS, = Pd, = Br; : = Bu PrPS, = Pt, = Cl) {systematic names: (-butyl-diiso-propyl-phosphine selenide-κ)di-chlorido-palladium(II), [PdCl(CHPSe)] (), (di--butyl-iso-propyl-phosphine selenide-κ)di-chloridopalladium(II), [PdCl(CHPSe)] (), di-bromido-(di--butyl-iso-propyl-phosphine selenide-κ)palladium(II), [PdBr(CHPSe)] (), di-bromido-(di--butyl-iso-propyl-phosphine sulfide-κ)palladium(II), [PdBr(CHPS)] (), di-chlorido-(di--butyl-iso-propyl-phosphine sulfide-κ)palladium(II), [PdCl(CHPS)] ()} all display a configuration with square-planar geometry at the metal atom. Compounds and are isotypic. The mol-ecules of and display crystallographic inversion symmetry; compound involves two independent mol-ecules, each with inversion symmetry but with differing orientations of the tri-alkyl-phosphane groups.
View Article and Find Full Text PDFAsymmetric copper-catalyzed hydrophosphinylation of ethynylazaarenes to access -chiral 2-azaaryl-ethylphosphine oxides.
Chem Sci
March 2025
School of Chemistry and Chemical Engineering, Henan Normal University Xinxiang Henan 453007 P. R. China
We report a cost-effective approach for the enantioselective hydrophosphinylation of ethynylazaarenes utilizing a chiral copper catalytic platform. This strategy efficiently converts racemic secondary phosphine oxides (SPOs) into -chiral tertiary phosphine oxides (TPOs) bearing functionalized olefin substituents with azaarene moieties, achieving high yields and exceptional enantioselectivities. These adducts serve as crucial intermediates in the development of valuable chiral 1,5-hybrid ,-ligands.
View Article and Find Full Text PDFEnhanced Photoluminescence Emission and Thermal Stability in Pt1Ag31 nanocluster from Introduced Secondary Phosphine Oxide Functionalized ligand.
Chem Asian J
March 2025
Anhui University, Institutes of Physical Science and Information Technology, 230601, CHINA.
Surface ligands significantly influence the optical properties and stability of metal nanoclusters. In this study, we synthesized [Pt1Ag31(S-Adm)16(DPPM)3(DPPMO)Cl3](SbF6)4 (Pt1Ag31-DPPMO). Compared to [Pt1Ag31(S-Adm)16(DPPM)3Cl3](SbF6)4 (Pt1Ag31), the introduction of secondary phosphine oxide ligand, DPPMO, results in Pt1Ag31-DPPMO exhibiting enhanced photoluminescent properties in both solution and solid states, as well as improved stability and electron-withdrawing ability.
View Article and Find Full Text PDFRhodium-Catalyzed Asymmetric Access to P-Chiral Triarylphosphine Oxides via Insertion of P-H Bonds into Carbenes.
Angew Chem Int Ed Engl
March 2025
Shaanxi Normal University, School of Chemistry and Chemical Engineering, West Changan Ave., 710062, Xi'an, CHINA.
While significant progress has been made in enantioselective insertion of carbenes into heteroatom-hydrogen bonds, this chemistry is predominantly restricted to construction of carbon-based chirality. The asymmetric insertion of carbenes into P-H that delivers P-chiral products remains untouched. We herein report rhodium(I)-catalyzed enantioselective synthesis of P-chiral triarylphosphine oxides via asymmetric C-P coupling of a secondary phosphine oxide (SPO) with diazonaphthoquinone.
View Article and Find Full Text PDFAnharmonicity and vibrational Stark fields in phosphinic acid dimers.
Phys Chem Chem Phys
March 2025
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India.
Phosphinic acid is unique among oxyacids of phosphorus, as it has the ability to form cyclic dimers intermolecular hydrogen bonding, analogous to carboxylic acid dimers with exceptional stability and higher dimerization enthalpies due to stronger hydrogen bonding interactions. The strength of the hydrogen bond with different combinations of substituents on the monomeric units can be effectively studied by evaluation of electric fields along the hydrogen-bonded OH donor groups. The correlation between OH stretch vibrational frequency and electric field was linear with average Stark tuning rates of 45.
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