Enhanced Photostability of a Ruthenium(II) Polypyridyl Complex under Highly Oxidizing Aqueous Conditions by Its Partial Inclusion into a Cyclodextrin

Farràs, Pau; Waller, Helen; Benniston, Andrew C.

doi:10.1002/chem.201503485

Cited by 5 publications

(3 citation statements)

References 37 publications

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“…A great variety of inclusion compounds of cyclodextrins with platinum-group metal complexes as guests have been synthesized and used in catalytic processes − or bioactivity studies. − In 1985 Stoddart and co-workers for the first time used cyclodextrins as encapsulatory vehicles for platinum(II) complexes. , The authors demonstrated that cyclobutane-1,1-dicarboxylatodiammine–platinum(II) ([Pt(NH 3 ) 2 (CBDCA)] forms a 1:1 adduct with α-CD in aqueous solution as well as in the solid state. The adduct is stabilized by N–H···O hydrogen-bonding interactions between the two NH 3 ligands with the secondary hydroxyl groups on α-CD as well as hydrophobic interactions resulting from penetration of the cyclobutane ring of the complex into the α-CD cavity.…”

Section: Inclusion Complexes Of Native Cyclodextrins With Organometal...mentioning

confidence: 99%

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science

2017

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Readily available cyclodextrins (CDs) with an inherent hydrophobic internal cavity and hydrophilic external surface are macrocyclic entities that display a combination of molecular recognition and complexation properties with vital implications for host-guest supramolecular chemistry. While the host-guest chemistry of CDs has been widely recognized and led to their exploitation in a variety of important functions over the last five decades, these naturally occurring macrocyclic systems have emerged only recently as promising macrocyclic molecules to fabricate environmentally benign functional nanomaterials. This review surveys the development in the field paying special attention to the synthesis and emerging uses of various unmodified CD-metal complexes and CD-inorganic nanoparticle systems and identifies possible future directions. The association of a hydrophobic cavity of CDs with metal ions or various inorganic nanoparticles is a very appealing strategy for controlling the inorganic subunits properties in the very competitive water environment. In this review we provide the most prominent examples of unmodified CDs' inclusion complexes with organometallic guests and update the research in this field from the past decade. We discuss also the coordination flexibility of native CDs to metal ions in CD-based metal complexes and summarize the progress in the synthesis and characterization of CD-metal complexes and their use in catalysis and sensing as well as construction of molecular magnets. Then we provide a comprehensive overview of emerging applications of native CDs in materials science and nanotechnology. Remarkably, in the past few years CDs have appeared as attractive building units for the synthesis of carbohydrate metal-organic frameworks (CD-MOFs) in a combination of alkali-metal cations. The preparation of this new class of highly porous materials and their applications in the separation of small molecules, the loading of drug molecules, as well as efficient host templates in the construction of nanomaterials with the desired functionality, including the first-in-class devices including sensors and memristors, are highlighted. Finally, CDs as well-known "green" molecular hosts have also been used as ideal functional molecules to improve the solubility, stability, and bioavailability of inorganic nanoparticles. In this regard, we demonstrate various strategies for the preparation of native CDs-modified inorganic nanomaterials such as metal, metal oxide, and semiconductor and magnetic nanoparticles, aiming to take advantage of both the controlled properties of the inorganic core and the controlled properties of the coating molecules. The functionalization of a CD hydrophobic cavity with an inorganic nanoparticle is very prospective for the development of novel catalytic systems and new tools for highly selective and sensitive sensing platforms for various targets.

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Section: Inclusion Complexes Of Native Cyclodextrins With Organometal...mentioning

confidence: 99%

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science

2017

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“…platinum(II) anticancer complexes such as carboplatin, 13 metallocene dihalides, [14][15][16][17] aromatic ruthenium complexes, 18 mixed sandwich complexes, 19 and numerous half-sandwich metal carbonyl and cyano complexes. 12,20 Encapsulation can affect the geometry of the guest, 21 its solubility and bioavailability, [22][23][24] thermal stability, 25,26 reactivity, 27,28 photostability, 29 photoluminescence, 30,31 and electrochemical 8,19,32,33 behaviour. These changes can be advantageous for application of OM@CD complexes as catalysts, [34][35][36] metallodrug delivery systems, 9,10,13,16,20,[22][23][24] supramolecular materials for opto-electronics, 37,38 electrochemical biosensors, 39,40 and molecular machines and switches.…”

Section: Introductionmentioning

confidence: 99%

Solid-state study of the structure and host–guest chemistry of cucurbituril-ferrocene inclusion complexes

et al. 2016

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Inclusion complexes of ferrocene (Fc) with cucurbit[n]urils (n = 7, 8) have been prepared via a rapid microwave-assisted hydrothermal approach. Solids were isolated and characterised by elemental analysis, powder X-ray diffraction (PXRD), spectroscopic, and thermoanalytical methods. The UV-Vis spectra support the presence of Fc in Fc@CB7 and a mixture of Fc and ferrocenium ions in Fc@CB8. Partial oxidation of Fc to Fc takes place in situ mainly due to the presence of acid of crystallisation in CB8. On the basis of PXRD, the complex Fc@CB8 is classified into an isostructural series that is formed by several CB8-containing compounds that crystallise in the space group I4/a and have similar unit cell dimensions and CB8 packing motifs. The FT-IR and Raman spectra of Fc@CB7 are compared with those of the CB7 host and the Fc guest starting materials, revealing significant frequency shifts of some Fc-centered vibrational modes upon complexation. Blueshifts of the Fe-Cp stretching and ring tilt bands are attributed to encapsulation of Fc monomers in a constrained environment, leading to restricted motion effects and/or a change in the Fc conformation from staggered to eclipsed. The absence of comparable shifts for Fc@CB8 point to a weaker host-guest interaction as a consequence of the larger cavity size. The different host-guest interactions are also evident through a comparison of the C{H} CP MAS NMR spectra. Thermogravimetric analysis for the inclusion compounds reveals that sublimation of Fc is inhibited by molecular encapsulation to the extent that oxidative decomposition of the organoiron species takes place concurrently with cucurbituril decomposition, leading to the formation of hematite, α-FeO.

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“…Nowadays the applications of cyclodextrin-ruthenium supramolecular systems are largely spread across many fields. Examples include molecular devices such as single or polynuclear fluorescence sensors (Zhang et al 2015;Chen et al 2013) and CD-stabilised Ru(II) photosensitizers for dye-sensitized solar cells (Farras et al 2016) or cyclodextrin metallosurfactants (M = Ru(II)) for gene therapy (Lebron et al 2015;Iza et al 2015). In antitumoral chemotherapy, ruthenium complexes make a strong claim as alternatives to platin compounds, for their more versatile ligand-exchange abilities, redox properties (?2 and ?3 oxidation states accessible in vivo) and octahedral geometry (instead of planar four-coordinated Pt) (Bergamo et al 2012).…”

Section: Introductionmentioning

confidence: 99%

Supramolecular adducts of native and permethylated β-cyclodextrins with (2,2′-dipyridylamine)chlorido(1,4,7-trithiacyclononane)ruthenium(II) chloride: solid-state and biological activity studies

et al. 2017

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The complex [([9]aneS 3 )Ru II (dipa)Cl]Cl (1, where dipa = 2,2 0 -dipyridylamine) was included into native b-cyclodextrin (b-CD) and permethylated b-CD (TRIMEB) by co-dissolution followed by solvent removal. Two adducts were obtained with a 1:1 host:guest stoichiometry. Solid-state studies of the guest comprised collecting the single-crystal structure of its 3.5 hydrate form and also powder diffraction on the remaining bulk material, showing it is isotypical with the harvested crystal for X-ray analysis. Solid-state studies of the cyclodextrin adducts were carried out by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), 13 C{ 1 H} CP/MAS NMR and FTIR spectroscopies. Biological studies on 1 and its adducts comprised the evaluation of the shift caused by 1 on the melting temperature of DNA (DT m ), as well as the evaluation of cytotoxicity by the MTT assay on the osteosarcoma MG-63 cell line. 1414MG-63 cell line. m, 1356MG-63 cell line. m, 1337MG-63 cell line. m, 1299MG-63 cell line. m, 1273MG-63 cell line. w, 1261MG-63 cell line. w, 1240MG-63 cell line. m, 1159 s, 1123 m, 1080 s, 1027 vs, 1000 s, 947 m, 935 m, 910 w, 848 m, 827 w, 775 m, 763 m, 709 m, 609 m, 576 m, 532 m, 440 w, 420 w, 402 w, 369 vw, 355 vw, 335 vw, 329 vw, 324 vw, 303 w, 289 w.

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Enhanced Photostability of a Ruthenium(II) Polypyridyl Complex under Highly Oxidizing Aqueous Conditions by Its Partial Inclusion into a Cyclodextrin

Cited by 5 publications

References 37 publications

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science

Interactions of Native Cyclodextrins with Metal Ions and Inorganic Nanoparticles: Fertile Landscape for Chemistry and Materials Science

Solid-state study of the structure and host–guest chemistry of cucurbituril-ferrocene inclusion complexes

Supramolecular adducts of native and permethylated β-cyclodextrins with (2,2′-dipyridylamine)chlorido(1,4,7-trithiacyclononane)ruthenium(II) chloride: solid-state and biological activity studies

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