Water-soluble, luminescent iridium(iii)-ytterbium(iii) complexes using dipyrido[3,2-a:2',3'-c]phenazine derivatives as bridging units

Amino-substituted dipyrido[3,2-a:2',3'-c]phenazine (L(1)) and dimethyl-dipyrido[3,2-a:2',3'-c]phenazine (L(2)) have been investigated as: (i) chromophores in cyclen-based ligands for lanthanide(iii) ions; (ii) ancillary co-ligands in cyclometalated iridium(iii) complexes; (iii) bridging, linker units in covalently linked, water-soluble bimetallic lanthanide(iii) iridium(iii) hybrid complexes. The dipyrido[3,2-a:2',3'-c]phenazine (dppz) derivatives can act as sensitising chromophores (λ(ex) 400 nm) for Yb(iii), resulting in characteristic near-IR emission at 950-1050 nm. The incorporation of dppz-type ligands into cyclometalated Ir(III) complexes of the general type [Ir(epqc)(2)(L(n))](PF(6)) (where epqc = ethylphenylquinoline carboxylate) gave luminescent species with solvent-sensitive emission properties. Steady state and time-resolved luminescence measurements on the water-soluble d-f hybrid species showed that Yb(III) can be sensitised using visible light.     

A study of M-X-BR3 (M = Pt, Pd or Rh; X = Cl or I) interactions in square planar ambiphilic ligand complexes: structural, spectroscopic, electrochemical and computational comparisons with borane-free analogues

Reaction of [PtCl(2)(COD)] and [PtI(2)(COD)] with 2,7-di-tert-butyl-5-diphenylboryl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPB) afforded square planar [PtCl(2)(TXPB)] (1B) and [PtI(2)(TXPB)] (4B), both of which were crystallographically characterized. Single-crystal X-ray quality crystals were also obtained for [PdCl(2)(TXPB)] (2B; Emslie et al., Organometallics, 2008, 27, 5317) as 2B·2CH(2)Cl(2) and solvent-free 2B. Both the chloro and iodo TXPB complexes exhibit metal-halide-borane bridging interactions similar to those in previously reported [RhCl(CO)(TXPB)] (3B) and [RhI(CO)(TXPB)] (5B) (Emslie et al., Organometallics, 2006, 25, 583 and Inorg. Chem., 2010, 49, 4060). To facilitate a more detailed analysis of M-X-BR(3) (X = Cl and I) interactions, a borane-free analogue of the TXPB ligand, 2,7-di-tert-butyl-4-diphenylphosphino-9,9-dimethylthioxanthene (TXPH), was prepared. Reaction with [PtX(2)(COD)] (X = Cl or I), [PdCl(2)(COD)] and 0.5 [{RhCl(CO)(2)}(2)] provided square planar [PtCl(2)(TXPH)] (1H), [PdCl(2)(TXPH)] (2H), [RhCl(CO)(TXPH)] (3H) and [PtI(2)(TXPH)] (4H). M-Cl-BR(3) and M-I-BR(3) bonding in 1B-5B was then probed through the use of structural comparisons, IR and NMR spectroscopy, cyclic voltammetry, and DFT calculations (Slater-type orbitals, Mayer bond orders, Hirshfeld charges, fragment analysis, SCF deformation density isosurfaces, and energy decomposition analysis).     

Utilizing a copper MOF as a reagent in a solvent mediated reaction to form a topologically distinct MOF

Employing a semi-rigid di-1,2,4-triazole ligand leads to the formation of new MOFs [Cu(4)(L)(4)(SO(4))(4)]·4[Cu(H(2)O)(6)(SO(4))] (3) and [Cu(6)(L)(3)(SO(4))(5)(OH)(2)(H(2)O)(6)]·13H(2)O (4). The frameworks can be synthesized independently, but a reaction occurs in water wherein kinetic product 3 is used as a reagent to synthesize the topologically distinct thermodynamic product 4.     

The Development of Boronic Acids as Sensors and Separation Tools

Synthetic receptors for diols that incorporate boronic acid motifs have been developed as new sensors and separation tools. Utilizing the reversible interactions of diols with boronic acids to form boronic esters under new binding regimes has provided new hydrogel constructs that have found use as dye‐displacement sensors and electrophoretic separation tools; similarly, molecular boronic‐acid‐containing chemosensors were constructed that offer applications in the sensing of diols. This review provides a somewhat‐personal perspective of developments in boronic‐acid‐mediated sensing and separation, placed in the context of the seminal works of others in the area, as well as offering a concise summary of the contributions of the co‐authors in the area. DOI 10.1002/tcr.201200006     

A Comparison of the use of FTIR spectroscopy with DSC in the characterisation of melting and crystallisation in polycaprolactone

The infrared spectrum of polycaprolactone has been recorded as a function of temperature in the range where melting and crystallisation of the polymer can occur. Examination of the carbonyl band of the spectra reveals a clear morphological sensitivity; heating the semi-crystalline polymer through the melting region results in a decrease in the intensity of the crystalline component of the carbonyl band. Accordingly, there was a subsequent increase in intensity of the crystalline carbonyl band on cooling. To enable comparison of these findings with a more conventional method of thermal analysis, similar experiments were conducted using a differential scanning calorimeter. The heated ATR accessory adopted for use in the FTIR spectrometer imposed significant limitations in the range of possible heating and cooling rates, but when these rates were carefully matched between FTIR and DSC, close correlation between the melting point and onset of re-crystallisation was observed. The results confirm that FTIR can be used as an alternative, if more laborious, way of investigating melting and re-crystallisation.     

Chloride binding by a polyimidazolium macrocycle detected via fluorescence,NMR, and X-ray crystallography

Herein, we describe a macrocyclic polyimidazolium receptor that is preorganized for the binding of anionic guests, and particularly chloride. Additionally, diphenylimidazolium units were incorporated into this structure to enhance photophysical properties that were exploited for signal transduction of binding. In subsequent fluorescence binding studies, this receptor was found to bind a range of halides as well as phosphate with high affinity (K_a=1.8×10⁴, and 1.5×10⁴ for phosphate and chloride, respectively) in a competitive solvent mixture (1:1 water/acetonitrile). Results under these conditions were fitted to 1:1 binding curves, and indicated modest selectivity of the host for phosphate and chloride over other halides. Binding studies were also performed using ¹H NMR spectroscopy, during which the imidazolium C–H signal was observed to shift downfield upon titration with anions. These experiments were run in less polar solvent (1:9 water/acetonitrile), and could not be fitted to a 1:1 binding curve, suggesting higher order aggregates in this environment. Binding was further probed in the solid state by obtaining an X-ray crystal structure of receptor–iodide complex. In the resulting structure, two iodides were found to bind through interactions with two polyimidazolium hydrogens each. These results show that the described macrocycle is effective for anion-binding in competitive solvent, with modest selectivity for chloride over other halides, and that the nature of the binding interactions varies depending upon the solvent environment.     

Training the perception of Hindi dental and retroflex stops by native speakers of American English and Japanese

Perception of second language speech sounds is influenced by one's first language. For example, speakers of American English have difficulty perceiving dental versus retroflex stop consonants in Hindi although English has both dental and retroflex allophones of alveolar stops. Japanese, unlike English, has a contrast similar to Hindi, specifically, the Japanese /d/ versus the flapped /r/ which is sometimes produced as a retroflex. This study compared American and Japanese speakers' identification of the Hindi contrast in CV syllable contexts where C varied in voicing and aspiration. The study then evaluated the participants' increase in identifying the distinction after training with a computer-interactive program. Training sessions progressively increased in difficulty by decreasing the extent of vowel truncation in stimuli and by adding new speakers. Although all participants improved significantly, Japanese participants were more accurate than Americans in distinguishing the contrast on pretest, during training, and on posttest. Transfer was observed to three new consonantal contexts, a new vowel context, and a new speaker's productions. Some abstract aspect of the contrast was apparently learned during training. It is suggested that allophonic experience with dental and retroflex stops may be detrimental to perception of the new contrast.