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Simon C. Rawle

Bio: Simon C. Rawle is an academic researcher from University of Oxford. The author has contributed to research in topics: Thioether & 1,4,7-Trithiacyclononane. The author has an hindex of 4, co-authored 8 publications receiving 379 citations.

Papers
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Book ChapterDOI
TL;DR: In this paper, the synthesis, structural, and coordination chemistry of crown thioethers with both transition and p-block metal ions is reviewed comprehensively through December 1988, focusing on the electronic structures and redox properties induced in metal ions by coordination to crown thiosethers.
Abstract: The synthetic, structural, and coordination chemistry of crown thioethers with both transition and p-block metal ions is reviewed comprehensively through December 1988. Emphasis falls upon the electronic structures and redox properties induced in metal ions by coordination to crown thioethers. Examples include stabilization of mononuclear Rh(II), Pt(III), and low-spin octahedral Co(II). A subsidiary theme concerns the influence of ligand conformation in determining both the binding efficacy and the qualitative coordination chemistry associated with a given crown thioether. The review concludes with a view toward potential future applications of crown thioethers in catalysis, in sequestration or biological delivery of heavy metal ions, and in fundamental studies directed toward rational design of ligands.

205 citations

Journal ArticleDOI
TL;DR: In this paper, the coordination chemistry of the crown thioethers 1,4,7-trithiacyclonononane (9S3), 1,5,9-trityclododecane (12S3) with Ag(I) has been investigated by structural and electrochemical methods.
Abstract: The coordination chemistry of the three crown thioethers 1,4,7-trithiacyclononane (9S3), 1,5,9-trithiacyclododecane (12S3), and 1,4,7,10,13,16-hexathiacyclooctadecane (18S6) with Ag(I) has been investigated by structural and electrochemical methods. The bis complex (Ag(9S3){sub 2})(CF{sub 3}SO{sub 3}) contains a six-coordinate Ag(I) ion with Ag-S distances ranging from 2.696 (2) to 2.753 (1) {angstrom}. Chemical or electrochemical oxidation yields (Ag(9S3){sub 2}){sup 2+}, which has been studied by optical and EPR methods. The halide adducts (Ag(9S3)Cl) and (Ag(18S6)Br) both contain a tetrahedral AgS{sub 3}X core. In the former case, 9S3 coordinates in a tridentate fashion to yield a discrete, monomeric complex. In the latter, 18S6 provides two thioethers to one Ag(I) and a third to another to yield a polymeric chain. In (Ag(12S3))(CF{sub 3}SO{sub 3}) {center dot} MeCN, each Ag(I) ion coordinates to three thioether groups (one from each of three independent 12S3 molecules) as well as a CF{sub 3}SO{sub 3}{sup {minus}} counterion to yield distorted-tetrahedral geometry. In turn, the three ligand S atoms coordinate to different Ag(I) ions to generate a network structure. These results highlight the profound influence of ligand conformation on the structure and solution chemistry of their complexes. Crystal data for (Ag(9S3){sub 2}) (CF{sub 3}SO{sub 3}), (Ag(18S6)Br), (Ag(9S3)Cl), and (Ag(12S3))(CF{sub 3}SO{sub 3}) {centermore » dot} MeCN are reported.« less

84 citations

Journal ArticleDOI
TL;DR: The Ni(II) complexes of 1,4,7,10,13,16-hexathioacyclooctadecane (18S6, hexathia-18-crown-6), 2,5,8-trithianonane, 1,5-9-tritiacyclododecane (12S3, trithia-12crown)-3, and 1.5,9, 13,17,21-hexathiacyclotetracosane (24S6) have been synthes
Abstract: The Ni(II) complexes of 1,4,7,10,13,16-hexathioacyclooctadecane (18S6, hexathia-18-crown-6), 2,5,8-trithianonane, 1,5,9-trithiacyclododecane (12S3, trithia-12-crown-3), and 1,5,9,13,17,21-hexathiacyclotetracosane (24S6, hexathia-24-crown-6) have been synthesized and characterized by single-crystal x-ray diffraction and electronic spectroscopy. Each of these complexes contains a high-spin (Ni(thioether)/sub 6/)/sup 2+/ cation with octahedral microsymmetry. Comparison of these complexes shows that within a conserved coordination sphere the different ring sizes (1) change the Ni-S distances by up to 0.05 /angstrom/, (2) affect the ligand field splitting by up to 10%, and (3) greatly influence the stability of the resulting complexes. Crystallographic data: (Ni(18S6))(picrate)/sub 2/, C/sub 24/H/sub 28/N/sub 6/O/sub 14/S/sub 6/Ni, monoclinic, space group C2/c (No. 15), a = 21.079 (6) /angstrom/, b = 8.685 (2) /angstrom/, c = 18.399 (5) /angstrom/, /beta/ = 93.63 (2)/degree/, Z = 4; (Ni(12S3)/sub 2/)(BF/sub 4/)/sub 2/, C/sub 18/H/sub 36/B/sub 2/F/sub 8/S/sub 6/Ni, orthorhombic, space group Pbca (No. 61), a = 19.369 (9) /angstrom/, b = 12.500 (5) /angstrom/, c = 11.862 (2) /angstrom/, Z = 4; (Ni(24S6))(BF/sub 4/)/sub 2/, C/sub 18/H/sub 36/B/sub 2/F/sub 8/S/sub 6/Ni, monoclinic, space group C2/c (No. 15), a = 13.744 (5) /angstrom/ b = 17.021 (5) /angstrom/, c = 13.801 (5) /angstrom/, /beta/ = 113.25 (3)/degree/, Z = 4. 37 refs., 5 figs., 9more » tabs.« less

55 citations

Journal ArticleDOI
TL;DR: In this article, 1,4,7-Trithiacyclononane (9S3) reacts with soluble silver(I) salts to form [Ag(9S 3)2]+, a monomeric complex that has a distorted octahedral structure and is readily oxidised to the silver(II) complex.
Abstract: 1,4,7-Trithiacyclononane (9S3) reacts with soluble silver(I) salts to form [Ag(9S3)2]+, a monomeric complex that has a distorted octahedral structure and is readily oxidised to the silver(II) complex.

37 citations


Cited by
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Journal ArticleDOI
TL;DR: Specific focus is placed on the development of new macrocycle hosts since 2010, coupled with considerations of the underlying principles of supramolecular chemistry as well as analytes of interest and common luminophores.
Abstract: There is great need for stand-alone luminescence-based chemosensors that exemplify selectivity, sensitivity, and applicability and that overcome the challenges that arise from complex, real-world media. Discussed herein are recent developments toward these goals in the field of supramolecular luminescent chemosensors, including macrocycles, polymers, and nanomaterials. Specific focus is placed on the development of new macrocycle hosts since 2010, coupled with considerations of the underlying principles of supramolecular chemistry as well as analytes of interest and common luminophores. State-of-the-art developments in the fields of polymer and nanomaterial sensors are also examined, and some remaining unsolved challenges in the area of chemosensors are discussed.

463 citations

Journal ArticleDOI

286 citations

Book ChapterDOI
TL;DR: In this paper, a summary of the coordination chemistry of homoleptic thioether macrocycles is presented, with emphasis on likely future developments and uses, and some unpublished results are discussed.
Abstract: Publisher Summary This chapter presents a summary that discusses the coordination chemistry of homoleptic thioether macrocycles critically, with emphasis on likely future developments and uses. Some unpublished results, mainly crystallographic data from laboratories, are discussed in this chapter. The coordination chemistry of thioether ligands has undergone a renaissance over the past five years. This has been because of the observation that cyclic thioethers can bind to a range of transition metal ions to form stable metal complexes. The properties of the M-S(thioether) bond can now be studied with a variety of metal centers, oxidation states, and coordination geometries. Another impetus for the study of the coordination chemistry of crown thioethers stems from the role of thioether binding in biological systems, such as d-biotin (involving tetrahydrothiophene), and blue copper proteins, such as plastocyanin and azurin (involving methionine). The high-yield syntheses of macrocyclic polyoxoethers are characterized by the strong template effects that arise from oxygen coordination by alkali metal ions during cyclization of polyoxo units. The parallel between the binding of soft transition metal ions by soft cyclic thioether ligands and the binding of hard main-group metal ions (Group IA and IIA) by hard cyclic oxyether ligands is presented.

280 citations

Book ChapterDOI
TL;DR: In this paper, the synthesis, structural, and coordination chemistry of crown thioethers with both transition and p-block metal ions is reviewed comprehensively through December 1988, focusing on the electronic structures and redox properties induced in metal ions by coordination to crown thiosethers.
Abstract: The synthetic, structural, and coordination chemistry of crown thioethers with both transition and p-block metal ions is reviewed comprehensively through December 1988. Emphasis falls upon the electronic structures and redox properties induced in metal ions by coordination to crown thioethers. Examples include stabilization of mononuclear Rh(II), Pt(III), and low-spin octahedral Co(II). A subsidiary theme concerns the influence of ligand conformation in determining both the binding efficacy and the qualitative coordination chemistry associated with a given crown thioether. The review concludes with a view toward potential future applications of crown thioethers in catalysis, in sequestration or biological delivery of heavy metal ions, and in fundamental studies directed toward rational design of ligands.

205 citations