Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR-II Multiplex Imaging

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Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR-II Multiplex Imaging. / Bădescu-Singureanu, Codruţa C.; Nizovtsev, Anton S.; Pecoraro, Vincent L. et al.

In: Angewandte Chemie - International Edition, Vol. 64, No. 3, e202416101, 15.01.2025.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{aeb784e6e59b4e8bbb648d6c73b269f6,

title = "Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR-II Multiplex Imaging",

abstract = "Multiplex imaging in the second near-infrared window (NIR-II, 1000–1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real-time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric LnIII/GaIII metallacrowns bearing RuII polypyridyl complexes, LnRu-3 (Ln=YIII, YbIII, NdIII, ErIII). Relaxed structures of YRu-3 in the ground and the excited electronic states have been calculated using dispersion-corrected density functional theory methods. Detailed photophysical studies of LnRu-3 have demonstrated that characteristic emission signals of YbIII, NdIII and ErIII in the NIR-II range can be sensitized upon excitation in the visible range through RuII-centered metal-to-ligand charge transfer (MLCT) states. We have also showed that these NIR-II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue-mimicking phantoms. This work opens unprecedented perspectives for NIR-II multiplex imaging using LnIII-based molecular compounds.",

keywords = "lanthanide, metal-to-ligand charge transfer, metallacrown, near-infrared luminescence, ruthenium",

author = "B{\u a}descu-Singureanu, {Codru{\c t}a C.} and Nizovtsev, {Anton S.} and Pecoraro, {Vincent L.} and St{\'e}phane Petoud and Eliseeva, {Svetlana V.}",

note = "This study has received funding from the EMERGEN-CE@INC2022 program, and in part from the Ligue R{\'e}gion-ale Contre le Cancer (Comit{\'e}s du Loiret, d{\textquoteright}Eure-et-Loir, duLoir-et-Cher and de la Sarthe), the network “Mol{\'e}culesmarines, m{\'e}tabolisme et cancer” from the Canc{\'e}rop{\^o}leGrand Ouest, the R{\'e}gion Centre-Val de Loire and the U.S.National Science Foundation under the grant CHE-1664964.S.P. acknowledges support from the Institut National de laSant{\'e} et de la Recherche M{\'e}dicale (Inserm). A.S.N. isgrateful to the French Embassy in Russia for the Metchni-kov scholarship. V.L.P. and A.S.N. acknowledge supportfrom Le Studium Loire Valley Institute for AdvancedStudies (Research Professorship and Guest Researcherprograms, respectively). The authors thank the MO2VING-MS and MO2VING-NMR facilities (Orl{\'e}ans, France).Authors are also grateful to Drs. Brayan Roulier andDimitrije Mara for their help with preliminary experiments.",

year = "2025",

month = jan,

day = "15",

doi = "10.1002/anie.202416101",

language = "English",

volume = "64",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons Inc.",

number = "3",

}

RIS

TY - JOUR

T1 - Enabling Visible Light Sensitization of YbIII, NdIII and ErIII in Dimeric LnIII/GaIII Metallacrowns through Functionalization with RuII Complexes for NIR-II Multiplex Imaging

AU - Bădescu-Singureanu, Codruţa C.

AU - Nizovtsev, Anton S.

AU - Pecoraro, Vincent L.

AU - Petoud, Stéphane

AU - Eliseeva, Svetlana V.

N1 - This study has received funding from the EMERGEN-CE@INC2022 program, and in part from the Ligue Région-ale Contre le Cancer (Comités du Loiret, d’Eure-et-Loir, duLoir-et-Cher and de la Sarthe), the network “Moléculesmarines, métabolisme et cancer” from the CancéropôleGrand Ouest, the Région Centre-Val de Loire and the U.S.National Science Foundation under the grant CHE-1664964.S.P. acknowledges support from the Institut National de laSanté et de la Recherche Médicale (Inserm). A.S.N. isgrateful to the French Embassy in Russia for the Metchni-kov scholarship. V.L.P. and A.S.N. acknowledge supportfrom Le Studium Loire Valley Institute for AdvancedStudies (Research Professorship and Guest Researcherprograms, respectively). The authors thank the MO2VING-MS and MO2VING-NMR facilities (Orléans, France).Authors are also grateful to Drs. Brayan Roulier andDimitrije Mara for their help with preliminary experiments.

PY - 2025/1/15

Y1 - 2025/1/15

N2 - Multiplex imaging in the second near-infrared window (NIR-II, 1000–1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real-time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric LnIII/GaIII metallacrowns bearing RuII polypyridyl complexes, LnRu-3 (Ln=YIII, YbIII, NdIII, ErIII). Relaxed structures of YRu-3 in the ground and the excited electronic states have been calculated using dispersion-corrected density functional theory methods. Detailed photophysical studies of LnRu-3 have demonstrated that characteristic emission signals of YbIII, NdIII and ErIII in the NIR-II range can be sensitized upon excitation in the visible range through RuII-centered metal-to-ligand charge transfer (MLCT) states. We have also showed that these NIR-II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue-mimicking phantoms. This work opens unprecedented perspectives for NIR-II multiplex imaging using LnIII-based molecular compounds.

AB - Multiplex imaging in the second near-infrared window (NIR-II, 1000–1700 nm) provides exciting opportunities for more precise understanding of biological processes and more accurate diagnosis of diseases by enabling real-time acquisition of images with improved contrast and spatial resolution in deeper tissues. Today, the number of imaging agents suitable for this modality remains very scarce. In this work, we have synthesized and fully characterized, including theoretical calculations, a series of dimeric LnIII/GaIII metallacrowns bearing RuII polypyridyl complexes, LnRu-3 (Ln=YIII, YbIII, NdIII, ErIII). Relaxed structures of YRu-3 in the ground and the excited electronic states have been calculated using dispersion-corrected density functional theory methods. Detailed photophysical studies of LnRu-3 have demonstrated that characteristic emission signals of YbIII, NdIII and ErIII in the NIR-II range can be sensitized upon excitation in the visible range through RuII-centered metal-to-ligand charge transfer (MLCT) states. We have also showed that these NIR-II signals are unambiguously detected in an imaging experiment using capillaries and biological tissue-mimicking phantoms. This work opens unprecedented perspectives for NIR-II multiplex imaging using LnIII-based molecular compounds.

KW - lanthanide

KW - metal-to-ligand charge transfer

KW - metallacrown

KW - near-infrared luminescence

KW - ruthenium

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85208189046&origin=inward&txGid=c72026defc40338130daf48b6277f8a9

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001357621700001

UR - https://www.elibrary.ru/item.asp?id=73788253

UR - https://www.mendeley.com/catalogue/9e15eadf-7b34-355b-a507-1b9d44c77cfd/

U2 - 10.1002/anie.202416101

DO - 10.1002/anie.202416101

M3 - Article

C2 - 39288073

VL - 64

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 3

M1 - e202416101

ER -

ID: 61245683