91997-32-9Relevant articles and documents
Anion Recognition in Water by Charge-Neutral Halogen and Chalcogen Bonding Foldamer Receptors
Borissov, Arseni,Marques, Igor,Lim, Jason Y.C.,Félix, Vítor,Smith, Martin D.,Beer, Paul D.
, p. 4119 - 4129 (2019/03/07)
A novel strategy for the recognition of anions in water using charge-neutral σ-hole halogen and chalcogen bonding acyclic hosts is demonstrated for the first time. Exploiting the intrinsic hydrophobicity of halogen and chalcogen bond donor atoms integrated into a foldamer structural molecular framework containing hydrophilic functionalities, a series of water-soluble receptors was constructed for an anion recognition investigation. Isothermal titration calorimetry (ITC) binding studies with a range of anions revealed the receptors to display very strong and selective binding of large, weakly hydrated anions such as I- and ReO4-. This is achieved through the formation of 2:1 host-guest stoichiometric complex assemblies, resulting in an encapsulated anion stabilized by cooperative, multidentate, convergent σ-hole donors, as shown by molecular dynamics simulations carried out in water. Importantly, the combination of multiple σ-hole-anion interactions and hydrophobic collapse results in I- affinities in water that exceed all known σ-hole receptors, including cationic systems (β2 up to 1.68 × 1011 M-2). Furthermore, the anion binding affinities and selectivity trends of the first example of an all-chalcogen bonding anion receptor in pure water are compared with halogen bonding and hydrogen bonding receptor analogues. These results further advance and establish halogen and chalcogen bond donor functions as new tools for overcoming the challenging goal of anion recognition in pure water.
Synthesis of extended, π-conjugated isoindolin-1-ones
Bubar, Alex,Estey, Paula,Lawson, Michael,Eisler, Sara
experimental part, p. 1572 - 1578 (2012/04/04)
The synthesis and characterization of extended, conjugated molecules containing isoindolinone units was explored. Nucleophilic cyclizations between an amide and an alkyne were found to be an efficient method of producing the desired isoindolin-1-ones in h
The synthesis of singlet ground state derivatives of non-Kekule polynuclear aromatics
Allinson, Graeme,Bushby, Richard J.,Jesudason, Malini V.,Paillaud, Jean-Louis,Taylor, Norman
, p. 147 - 156 (2007/10/03)
It is known that a two-electron reduction of tetrabutylammonium 3,4-dioxo-4H,8H-dibenzo[cd,mn]pyren12-olate gives a trioxy (tri-O-) derivative of the non-Kekule polynuclear aromatic compound dibenzo[cd,mn]pyrene (triangulene). This derivative is stable in solution and, like triangulene itself, has a triplet ground state. In exploring the generality of this strategy for the synthesis of high-spin derivatives of non-Kekule polynuclear aromatic compounds we have investigated two electron reductions of 4,8-dioxo-4H,8H-dibenzo[cd,mn]pyrene (to give a dioxy derivative of triangulene), 7,8-dioxo-7H,8H-dibenzo[de,hi]naphthacene (to give a dioxy derivative of dibenzo[de,hi]naphthacene) and 7,9-dioxo-7H,9H-dibenzo[de,jk]pentacene (to give a dioxy derivative of dibenzo[de,jk]pentacene). Dibenzo-[cd,mn]pyrene (triangulene), dibenzo[de,hi]naphthacene and dibenzo[de,jk]pentacene should all have triplet ground states, but the presence of two O- substituents on these aromatic nuclei will (just) lift the degeneracy of the putative singly occupied molecular orbitals. We have shown that the splitting this produces is sufficient to ensure that all of these dioxy derivatives have singlet ground states. Hence the strategy employed for making and stabilising triplet triangulene as its trioxy derivative does not provide a paradigm for other high-spin non-Kekule polynuclear aromatics. The reduction reactions were studied by cyclic voltammetry, by UV-VIS spectroscopy, and by EPR spectroscopy. Improved synthetic routes are described for 7,8-dioxo-7H,8H-dibenzo[de,hi]naphthacene and for 7,9-dioxo-7H,9H-dibenzo[de,jk]-pentacene. Violent explosions were encountered in attempts to repeat the literature procedure for the synthesis of 4,6-dichlorobenzene-1,3-dicarboxylic acid.