Naphthalene Diimide and Bis-Heteroleptic Ru(II) Complex-Based Hybrid Molecule with 3-in-1 Functionalities.

Multipurpose applications of a newly developed homobimetallic Ru(II) complex, Ru-NDI[PF], which incorporates 1,10-phenanthroline and triazole-pyridine ligands and linked via a (-CH-) spacer to the reputed anion-π interacting NDI system, are described. Solution-state studies of the bimetallic complex, including EPR, PL, UV-vis, and NMR experiments, reveal two sequential one-electron transfers to the NDI unit, generating NDI⋅ and NDI in the presence of F selectively. This process inhibits the primary electron transfer from Ru(II) to the NDI unit, thereby allowing the MLCT-based emission of the complex to be recovered, resulting in a corresponding ten-fold increase in luminescence intensity.

Selective recognition and extraction of iodide from pure water by a tripodal selenoimidazol(ium)-based chalcogen bonding receptor.

A selenium-based tripodal chalcogen bond (ChB) donor TPI-3Se is demonstrated for the recognition and extraction of I from 100% water medium. NMR and ITC studies with the halides reveal that the ChB donor selectively binds with the large, weakly hydrated I. Interestingly, I crystallizes out selectively in the presence of other halides supporting the superiority of the selective recognition of I.

Development and Application of Ruthenium(II) and Iridium(III) Based Complexes for Anion Sensing.

Improvements in the design of receptors for the detection and quantification of anions are desirable and ongoing in the field of anion chemistry, and remarkable progress has been made in this direction. In this regard, the development of luminescent chemosensors for sensing anions is an imperative and demanding sub-area in supramolecular chemistry. This decade, in particular, witnessed advancements in chemosensors based on ruthenium and iridium complexes for anion sensing by virtue of their modular synthesis and rich chemical and photophysical properties, such as visible excitation wavelength, high quantum efficiency, high luminescence intensity, long lifetimes of phosphorescence, and large Stokes shifts, etc.

Merging Photocatalytic C-O Cross-Coupling for α-Oxycarbonyl-β-ketones: Esterification of Carboxylic Acids via a Decarboxylative Pathway.

Herein, the first merged photocatalytic pathway for the C-O cross-coupled esterification of carboxylic acids to α-oxycarbonyl-β-ketones has been demonstrated. Decarboxylation of α,β-unsaturated acids promotes the formation of the β-ketone fragment of the desired product. Water as the source of oxygen for the ketone segment and aerial oxygen as an oxidant make the present synthetic methodology green and sustainable.

Room-Temperature Synthesis of 1,3,5-Tri()aryl Benzene from Nitroalkenes Using Pd(OAc): Complete Mechanistic and Theoretical Studies.

Herein, a room-temperature catalytic pathway for 1,3,5-tri()aryl derivatives from nitroalkenes using simple Pd(OAc) is presented. This newly developed C-C bond-forming methodology takes place in a cascade manner with the initial pallado-Morita-Baylis-Hillman (MBH) type adduct. The broad substrate scopes, functional group tolerance, and different aryl-substituted benzene derivatives make this methodology more attractive.

A Bis-heteroleptic Imidazolium-bipyridine Functionalized Iridium(III) Complex for Fluorescence Lifetime-based Recognition and Sensing of Phosphates.

A new Ir based 3,3'-([2,2'-bipyridine]-5,5'-diylbis(methylene))bis(1-ethyl-1H-imidazol-3-ium) functionalized receptor Ir-1 has been synthesized for selective recognition, sensing and as a lifetime based sensor for H PO and HP O in acetonitrile. An increase in the lifetime (τ) from 0.03543 μs to 0.

Influence of Triazole Substituents of Bis-Heteroleptic Ru(II) Probes toward Selective Sensing of Dihydrogen Phosphate.

A series of seven new bis-heteroleptic Ru(II) probes (-) along with two previously reported probes ( and ) containing a similar anion binding triazole unit (hydrogen bond donor) functionalized with various substituents are employed in a detailed comparative investigation for the development of superior selective probes for HPO. Various solution- and solid-state studies, such as H-DOSY NMR, dynamic light scattering (DLS), single-crystal X-ray crystallography, and transmission electron microscopy (TEM), have established that the selective sensing of HPO by this series of probes is primarily due to supramolecular aggregation driven enhancement of MLCT emission. Intestingly, and , having an electron-deficient (π-acidic) aromatic pentafluorophenyl substituent are found to be superior probes for HPO in comparison to the other aryl- and polyaromatic-substituted analogues (-, , and ), in terms of a higher enhancement of the MLCT emission band, a greater binding constant, and a lower detection limit.

Discriminative Behavior of a Donor-Acceptor-Donor Triad toward Cyanide and Fluoride: Insights into the Mechanism of Naphthalene Diimide Reduction by Cyanide and Fluoride.

A new molecular donor-acceptor-donor (D-A-D) triad, comprised of an electron deficient 1,4,5,8-naphthalene tetracarboxylic diimide (NDI) unit covalently connected to two flanking photosensitizers, i.e., a bis-heteroleptic Ru(II) complex of 1,10-phenanthroline and pyridine triazole hybrid ligand, is described.

Supramolecular Self-Assembly Driven Selective Sensing of Phosphates.

A new bis-heteroleptic Ru complex () with iodotriazole as the anion binding group along with the attached pyrene moiety is developed to investigate anion sensing properties and the origin of its selectivity toward a particular class of anions. Selective sensing of phosphates over other anions in both the solution and solid states by is clearly evident from the perturbation of the absorption band and a large degree of amplification of MLCT emission band in the presence of phosphates. Importantly, macroscopic investigation such as Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) indicated the formation of supramolecular architecture in the presence of dihydrogen phosphate via halogen bonding interaction and π-π stacking of pyrene moieties.

An integrated urea and halogen bond donor based receptor for superior and selective sensing of phosphates.

A new RuII based bis-heteroleptic ditopic receptor, 1[PF6]2 (C44H33F12IN10OP2Ru), having integrated anion binding iodotriazole (halogen bond donor) and urea units (-NH bond donor) is employed for selective sensing of phosphates (e.g., H2PO4- and HP2O73-).