Near-infrared phosphorescent materials have received significant attention due to their potential applications in bioimaging and diagnostics. Although, many types of organic phosphors with near-infrared emission have been developed, the low phosphorescence efficiency in aqueous solution hampers their practical applications in biological systems. Hence, there is an urgent need to develop near-infrared phosphorescent materials with high emission efficiency in aqueous media. Metallotweezers, based on d transition metal complexes, emerge as the potential candidates for realizing this objective. Specifically, metallotweezers, featuring two positively charged platinum(II) terpyridine and neutral gold(III) diphenylpyridine pincers on diphenylpyridine spacer, have been designed and synthesized, respectively. The pre-organization effect, rendered by the rigid spacer, enables the resulting metallotweezers to complex with each other, resulting in the formation of clipping complex. The synergistic rigidifying and shielding effects of clipping structure results in enhanced phosphorescent emission intensity. Concurrently, due to phase segregation between the clipping units and the polyethylene glycol tail, the clipping complex undergoes self-assembly in aqueous solution, resulting in phosphorescent emission in the near-infrared region. Overall, non-covalent clipping of metallotweezers illustrated in this study presents a new and effective approach toward near-infrared phosphorescent materials.
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http://dx.doi.org/10.1002/chem.202401022 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Sun Yat-Sen University, School of Chemistry and Chemical Engineering, 135 West Xingang Road, 510275, Guangzhou, CHINA.
Metal-organic complexes with long afterglow luminescence have attracted extensive attention due to potential applications in display, sensing and information security. However, most of the metal-organic complex long afterglow materials reported so far are limited to the use of UV light as the excitation source, and the ambiguity of the structure-activity relationship makes the development of metal-organic complexes extremely limited. Herein, a series of metal-organic complexes with ultralong emission lifetime is constructed by coordination assembly of Zn(II) with three isomers.
View Article and Find Full Text PDFNatl Sci Rev
February 2025
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.
Organic red/near-infrared (NIR) room-temperature phosphorescence (RTP) holds significant potential for autofluorescence-free bioimaging and biosensing due to its prolonged persistent luminescence and exceptional penetrability. However, achieving activatable red/NIR organic RTP probes with tunable emission in aqueous solution remains a formidable challenge. Here we report on aqueous organic RTP probes with red/NIR phosphorescence intensity and lifetime amplification.
View Article and Find Full Text PDFDalton Trans
January 2025
Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council of Italy (CNR), Via Piero Gobetti 101, 40129 Bologna, Italy.
The 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(II) polypyridine complex A (with the formula [Ru(dtbbpy)(azab-py)], where dtbbpy = 4,4'-di--butyl-2,2'-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy)] (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy)(ppy)], where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy)(naft-py)] (D), where the B-N unit of the azaborine ligand is replaced by a standard CC one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Institute of Molecular Functional Materials, State Key Laboratory of Synthetic Chemistry, and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, 999077, P. R. China.
Nano Lett
December 2024
College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
Nano-supramolecules based on artificial macrocycles can not only regulate assembly morphology but also boost phosphorescence resonance energy transfer (PRET). Herein, a water-soluble phosphorescence supramolecule was constructed from the hyaluronic acid-modified bromophenylpyridinium (HAPY), cucurbit[]uril (CB[], = 7/8), and energy acceptor phenyl-bridged phenothiazine derivatives, displaying efficient PRET and achieving near-infrared (NIR) phosphorescence by macrocyclic CB[] and the assembly confinements. As compared with weak phosphorescent nanofibers of HAPY/CB[7], the spherical nanoparticles of HAPY/CB[8] not only gave strong green phosphorescence with extended lifetime to 1.
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