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      Guest-host doped strategy for constructing ultralong-lifetime near-infrared organic phosphorescence materials for bioimaging

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          Abstract

          Organic near-infrared room temperature phosphorescence materials have unparalleled advantages in bioimaging due to their excellent penetrability. However, limited by the energy gap law, the near-infrared phosphorescence materials (>650 nm) are very rare, moreover, the phosphorescence lifetimes of these materials are very short. In this work, we have obtained organic room temperature phosphorescence materials with long wavelengths (600/657–681/732 nm) and long lifetimes (102–324 ms) for the first time through the guest-host doped strategy. The guest molecule has sufficient conjugation to reduce the lowest triplet energy level and the host assists the guest in exciton transfer and inhibits the non-radiative transition of guest excitons. These materials exhibit good tissue penetration in bioimaging. Thanks to the characteristic of long lifetime and long wavelength emissive phosphorescence materials, the tumor imaging in living mice with a signal to background ratio value as high as 43 is successfully realized. This work provides a practical solution for the construction of organic phosphorescence materials with both long wavelengths and long lifetimes.

          Abstract

          Though room-temperature phosphorescence (RTP) in organics is advantageous for bioimaging, designing materials that meet lifetime and wavelength emission requirements is challenging. Here, the authors us a guest-host doped strategy to construct RTP materials with ultralong-lifetime, NIR emission.

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          Stabilizing triplet excited states for ultralong organic phosphorescence.

          The control of the emission properties of synthetic organic molecules through molecular design has led to the development of high-performance optoelectronic devices with tunable emission colours, high quantum efficiencies and efficient energy/charge transfer processes. However, the task of generating excited states with long lifetimes has been met with limited success, owing to the ultrafast deactivation of the highly active excited states. Here, we present a design rule that can be used to tune the emission lifetime of a wide range of luminescent organic molecules, based on effective stabilization of triplet excited states through strong coupling in H-aggregated molecules. Our experimental data revealed that luminescence lifetimes up to 1.35 s, which are several orders of magnitude longer than those of conventional organic fluorophores, can be realized under ambient conditions. These results outline a fundamental principle to design organic molecules with extended lifetimes of excited states, providing a major step forward in expanding the scope of organic phosphorescence applications.
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            Activating efficient phosphorescence from purely organic materials by crystal design.

            Phosphorescence is among the many functional features that, in practice, divide pure organic compounds from organometallics and inorganics. Considered to be practically non-phosphorescent, purely organic compounds (metal-free) are very rarely explored as emitters in phosphor applications, despite the emerging demand in this field. To defy this paradigm, we describe novel design principles to create purely organic materials demonstrating phosphorescence that can be turned on by incorporating halogen bonding into their crystals. By designing chromophores to contain triplet-producing aromatic aldehydes and triplet-promoting bromine, crystal-state halogen bonding can be made to direct the heavy atom effect to produce surprisingly efficient solid-state phosphorescence. When this chromophore is diluted into the crystal of a bi-halogenated, non-carbonyl analogue, ambient phosphorescent quantum yields reach 55%. Here, using this design, a series of pure organic phosphors are colour-tuned to emit blue, green, yellow and orange. From this initial discovery, a directed heavy atom design principle is demonstrated that will allow for the development of bright and practical purely organic phosphors.
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              Room-temperature phosphorescence from organic aggregates

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                Author and article information

                Contributors
                yunxianglei@wzu.edu.cn
                xiaobhuang@wzu.edu.cn
                dingd@nankai.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                10 January 2022
                10 January 2022
                2022
                : 13
                : 186
                Affiliations
                [1 ]GRID grid.412899.f, ISNI 0000 0000 9117 1462, School of Chemistry and Materials Engineering, , Wenzhou University, ; Wenzhou, 325035 P. R. China
                [2 ]GRID grid.216938.7, ISNI 0000 0000 9878 7032, State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials, Ministry of Education, and College of Life Sciences, , Nankai University, ; Tianjin, 300071 China
                [3 ]GRID grid.43555.32, ISNI 0000 0000 8841 6246, School of Materials Science & Engineering, , Beijing Institute of Technology, ; Beijing, 10081 P. R. China
                Author information
                http://orcid.org/0000-0002-6584-9596
                http://orcid.org/0000-0003-0239-9601
                http://orcid.org/0000-0003-1873-6510
                Article
                27914
                10.1038/s41467-021-27914-0
                8748955
                35013474
                aeb4f969-291d-498f-af62-d5f12c3bb335
                © The Author(s) 2022

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 23 June 2021
                : 17 December 2021
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 22071184, 51961160730, 51873092, and 81921004
                Award Recipient :
                Categories
                Article
                Custom metadata
                © The Author(s) 2022

                Uncategorized
                biological fluorescence,nanophotonics and plasmonics,nanoparticles,imaging and sensing

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