Cadmium Dicyanoaurates and Their Reaction with Ammonia.

The synthesis and crystal structures of two anionic cadmium dicyanoaurate coordination polymers, [nBu4N]6[(Cd4Cl4)2(Au(CN)2)12][CdCl4] (TCCA) and [nBu4N]2[Cd(Au(CN)2)4], and their reaction with ammonia vapour is reported. TCCA and the isostructural [nBu4N]6[(Cd4Br4)2(Au(CN)2)12][CdBr4] form 3-D arrays with [Cd4X4]4+ (X=Cl, Br) cubane clusters linked from each octahedral Cd(II) centre by three bridging [Au(CN)2]- units. TCCA reacts with ammonia with concentrations of 1000 ppm or higher to give a product with a quantum yield of 0.88, while [nBu4N]2[Cd(Au(CN)2)4], which forms a 2-D anionic Cd[Au(CN)2]2 sheet structure with axially pendant [Au(CN)2]- units, reacts with concentrated ammonia vapour to generate Cd(NH3)2[Au(CN)2]2; this has a similar 2-D sheet structure but with axial NH3 units. Vibrational spectroscopy illustrated that the reaction of both Cd/[Au(CN)2]-based materials with ammonia proceeded by breaking Cd-NC bonds. For [nBu4N]2[Cd(Au(CN)2)4], this results in decomposition into [nBu4N][Au(CN)2] ⋅ 0.5H2O and Cd(NH3)2[Au(CN)2]2, while the reaction of ammonia with TCCA is reversible by heating the ammonia-bound sample above 110 °C. Cd[Au(CN)2]2 can be prepared by thermal removal of NH3 units from Cd(NH3)2[Au(CN)2]2.

Sequence-Defined Conjugated Oligomers in Donor-Acceptor Dyads.

Conjugated macromolecules have a rich history in chemistry, owing to their chemical arrangements that intertwine physical and electronic properties. The continuing study and application of these systems, however, necessitates the development of atomically precise models that bridge the gap between molecules, polymers, and/or their blends. One class of conjugated polymers that have facilitated the advancement of structure-property relationships is discrete, precision oligomers that have remained an outstanding synthetic challenge with only a handful of reported examples. Here we show the first synthesis of molecular dyads featuring sequence-defined oligothiophene donors covalently linked a to small-molecule acceptor. These dyads serve as a platform for probing complex photophysical interactions involving sequence-defined oligomers. This assessment is facilitated through the unprecedented control of oligothiophene length- and sequence-dependent arrangement relative to the acceptor unit, made possible by the incorporation of hydroxyl-containing side chains at precise positions along the backbone through sequence-defined oligomerizations. We show that both the oligothiophene sequence and length play complementary roles in determining the transfer efficiency of photoexcited states. Overall, the work highlights the importance of the spatial arrangement of donor-acceptor systems that are commonly studied for a range of uses, including light harvesting and photocatalysis.

Copper(II) Pyridyl Aminophenolates: Hypoxia-Selective, Nucleus-Targeting Cytotoxins, and Magnetic Resonance Probes.

Targeting the low-oxygen (hypoxic) environments found in many tumours by using redox-active metal complexes is a strategy that can enhance efficacy and reduce the side effects of chemotherapies. We have developed a series of CuII complexes with tridentate pyridine aminophenolate-based ligands for preferential activation in the reduction window provided by hypoxic tissues. Furthermore, ligand functionalization with a pendant CF3 group provides a 19 F spectroscopic handle for magnetic-resonance studies of redox processes at the metal centre and behaviour in cellular environments. The phenol group in the ligand backbone was substituted at the para position with H, Cl, and NO2 to modulate the reduction potential of the CuII centre, giving a range of values below the window expected for hypoxic tissues. The NO2 -substituted complex, which has the highest reduction potential, showed enhanced cytotoxic selectivity towards HeLa cells grown under hypoxic conditions. Cell death occurs by apoptosis, as determined by analysis of the cell morphology. A combination of 19 F NMR and ICP-OES indicates localization of the NO2 complex in HeLa cell nuclei and increased cellular accumulation under hypoxia. This correlates with DNA nuclease activity being the likely origin of cytotoxic activity, as demonstrated by cleavage of DNA plasmids in the presence of the CuII nitro complex and a reducing agent. Selective detection of the paramagnetic CuII complexes and their diamagnetic ligands by 19 F MRI suggests hypoxia-targeting theranostic applications by redox activation.

Zinc Tetracyanoplatinate: A Reversible Luminescence-Based Ammonia Sensor.

ZnPt(CN)4 was shown to be an effective material for ammonia sensing, and can be synthesized using either solution or mechanochemical methods. A combination of luminescence and Raman spectroscopy revealed that multiple species are involved in the reaction between ammonia and ZnPt(CN)4 . The crystal structure of one of these species, Zn(NH3 )2 Zn(NH3 )3 (Pt(CN)4 )2 , was elucidated. Detection of ammonia vapor down to 50 ppm in air was accomplished by monitoring the luminescence spectrum. The reaction between ZnPt(CN)4 and ammonia vapor is reversible, and can be cycled multiple times by either flowing air over the material or heating. ZnPt(CN)4 also has a relatively high thermal stability, decomposing only when heated above 420 °C.

Mixed Cu(i)/Au(i) coordination polymers as reversible turn-on vapoluminescent sensors for volatile thioethers.

Vapour-phase thioethers play an important role in a wide number of fields, including plant biology, chemical weapon disposal, and brewing but few sensor materials are known. The emissive coordination polymer Cu1/2Au1/2CN does not react with vapour phase dimethyl sulphide (DMS) or diethyl sulphide (DES) despite the independent synthesis of emissive [Cu1/2Au1/2CN]2(DMS) and [Cu1/2Au1/2CN]2(DES) from their constituent components in solution. However, the doped Cu2/3Au1/3CN rapidly reacts in the solid state with both of these vapour phase thioethers reversibly, with a change in emission from 380/560 nm to 460 nm (DMS) or 420 nm (DES), illustrating that doping the inactive parent Cu1/2Au1/2CN with Cu(i) generates an active sensor material. This response can be thermally cycled with little to no loss in functionality. [Cu1/2Au1/2CN]2(DMS), [Cu2/3Au1/3CN]2(DMS), and [Cu2/3Au1/3CN]2(DES) were structurally characterized as 3-D network structures supported by aurophilic interactions.