In this paper we report phosphorescent Pt(ii) complexes as monomers which can be directly incorporated into growing polymers. Due to the amphiphilic nature of the polymers they can self-assemble into micellar nanoparticles, where the phosphorescent Pt(ii) complexes can arrange selectively in the core or shell of the nanoparticles. The complexes enable dual orthogonal imaging, made possible by the heavy metal, which enhances the contrast for these micelles in electron microscopy and facilitates spin-orbit coupling that turns on microsecond lifetime luminescence.
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http://dx.doi.org/10.1039/c8cc06347h | DOI Listing |
Dalton Trans
January 2025
Department of Chemistry, Università degli Studi di Milano, via C. Golgi 19, I-20133 Milan, Italy.
The synthesis of novel highly phosphorescent N^C^N tridentate platinum(II)-complex-peptide nucleic acid (PNA) bioconjugates was accomplished through the solid-phase approach. Melting temperature measurements and circular dichroism spectroscopy studies demonstrated that these conjugates maintain the PNA ability to recognize complementary ssDNA and ssRNA, though the length of the spacer between the metal center and the PNA sequence affects their hybridization properties. Noteworthy, the conjugation of PNA to this family of Pt(II) complexes significantly enhanced the luminescent features of the organometallic moiety, leading to increased quantum yields (82.
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January 2025
College of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, P. R. China.
A series of carbazolylpyridine ()-based 6/5/6 Pt(II) complexes featuring tetradentate ligands with nitrogen or oxygen atoms as bridging groups was designed and synthesized, and the bridging nitrogen atoms were derived from acridinyl (Ac), azaaceridine (AAc) and carbazole (Cz). Systematic experimental and theoretical studies reveal that the ligand structures have a significant effect on the electrochemical, photophysical and excited state properties of these complexes. Their oxidation processes mainly occur on the carbazole-Pt moieties, whereas the reduction processes typically occur on the electron-deficient pyridine (Py) moieties.
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January 2025
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR 6302 CNRS, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France.
Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = -tolyl (1), mesityl (2), -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10-10 M), ionic strengths (0-0.
View Article and Find Full Text PDFACS Omega
December 2024
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Since the 1980s, pressure-sensitive paint (PSP) has been used as an optical pressure sensor for measuring surface pressure on aircraft models in wind tunnels. Typically, PSPs have utilized platinum(II)-5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)-porphyrin due to its high pressure sensitivity, phosphorescence lifetime of ∼50 μs, reasonable quantum yield of emission, and resistance to photo-oxidation. This work investigates the photophysics and electronic structure of metal complexes of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)-porphyrin, namely, Zn(II), Pd(II), and Ir(III), as potentially improved luminophores for polymer-based PSPs.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
School of Chemical Engineering, Sungkyunkwan University, 2066, Seobu-ro, Jangan-gu, Suwon-si, Gyeonggi-do 16419, Republic of Korea.
In this study, a tetradentate Pt(II) complex designed to have -heterocyclic carbene ligands modified with an anchor-shaped 2,6-diisopropylphenyl (dip) group is described to enhance molecular rigidity for narrow emission and high efficiency. The tetradentate ligand with the dip group significantly hinders steric interactions and restricts π-conjugation from benzocarbene, leading to shallow lowest unoccupied molecular orbital levels and a consequent reduction in the triplet metal-to-ligand charge transfer character. These structural modifications result in narrow emission spectra and enhanced efficiency for blue organic light-emitting diodes (OLEDs) over wide doping concentration ranges.
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