TY - JOUR

T1 - Stabilization of Octahedral Metal Halide Clusters by Host-Guest Complexation with γ-Cyclodextrin: Toward Nontoxic Luminescent Compounds

AU - Ivanov, Anton A.

AU - Haouas, Mohamed

AU - Evtushok, Darya V.

AU - Pozmogova, Tatiana N.

AU - Golubeva, Tatiana S.

AU - Molard, Yann

AU - Cordier, Stéphane

AU - Falaise, Clément

AU - Cadot, Emmanuel

AU - Shestopalov, Michael A.

N1 - Funding Information: The authors gratefully acknowledge financial support from LIA-CNRS CLUSPOM, the grant of the President of the Russian Federation (grant no. MD-123.2022.1.3), and the Ministry of Science and Higher Education of the Russian Federation (no. 121031700321-3). This work was also supported by public grants overseen by (i) University of Versailles Saint Quentin, (ii) CNRS, (iii) Region Île-de-France, (iv) and French National Research Agency (ANR) as part of the “Investissements d’Avenir” program (Labex charmmmat, ANR-11-LBX-0039-grant). Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/9/12

Y1 - 2022/9/12

N2 - γ-Cyclodextrin (γ-CD) interacts in aqueous solution with octahedral halide clusters Na2[{M6X8}Cl6] (M = Mo, W; X = Br, I) to form robust inclusion supramolecular complexes [{M6X8}Cl6@2γ-CD]2-. Single-crystal X-ray diffraction analyses revealed two conformational organizations within the adduct depending on the nature of the inner halide X within the {M6X8} core. Using 35Cl NMR and UV-vis as complementary techniques, the kinetics of the hydrolysis process were shown to increase with the following order: {W6I8} < {W6Br8} ≈ {Mo6I8} < {Mo6Br8}. The complexation with γ-CD drastically enhances the hydrolytic stability of luminescent [{M6X8}Cl6]2-cluster-based units, which was quantitatively proved by the same techniques. The resulting host-guest complexation provides a protective shell against contact with water and offers promising horizons for octahedral clusters in biology as revealed by the low dark cytotoxicity and cellular uptake.

AB - γ-Cyclodextrin (γ-CD) interacts in aqueous solution with octahedral halide clusters Na2[{M6X8}Cl6] (M = Mo, W; X = Br, I) to form robust inclusion supramolecular complexes [{M6X8}Cl6@2γ-CD]2-. Single-crystal X-ray diffraction analyses revealed two conformational organizations within the adduct depending on the nature of the inner halide X within the {M6X8} core. Using 35Cl NMR and UV-vis as complementary techniques, the kinetics of the hydrolysis process were shown to increase with the following order: {W6I8} < {W6Br8} ≈ {Mo6I8} < {Mo6Br8}. The complexation with γ-CD drastically enhances the hydrolytic stability of luminescent [{M6X8}Cl6]2-cluster-based units, which was quantitatively proved by the same techniques. The resulting host-guest complexation provides a protective shell against contact with water and offers promising horizons for octahedral clusters in biology as revealed by the low dark cytotoxicity and cellular uptake.

KW - Crystallography, X-Ray

KW - Magnetic Resonance Spectroscopy

KW - Molecular Conformation

KW - Water/chemistry

KW - gamma-Cyclodextrins/chemistry

UR - http://www.scopus.com/inward/record.url?scp=85137916959&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/83beafa6-8b1d-3f97-ba58-2270a5c59154/

U2 - 10.1021/acs.inorgchem.2c02468

DO - 10.1021/acs.inorgchem.2c02468

M3 - Article

C2 - 36041168

AN - SCOPUS:85137916959

VL - 61

SP - 14462

EP - 14469

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 36

ER -