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. Thus, this review aims to summarize the recent advances in the development of ruthenium(II) and iridium(III)-based complexes for their application as luminescent chemosensors for anion sensing. In addition, the focus was devoted to designing aspects of polypyridyl complexes of these two transition metals with different recognition motifs, which upon interacting with different inorganic anions, produces desirable quantifiable outputs.

Room-Temperature Synthesis of 1,3,5-Tri(het)aryl Benzene from Nitroalkenes Using Pd(OAc)2: Complete Mechanistic and Theoretical Studies.

Herein, a room-temperature catalytic pathway for 1,3,5-tri(het)aryl derivatives from nitroalkenes using simple Pd(OAc)2 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. Furthermore, the mechanistic understanding through isolation of intermediates and DFT studies of the catalytic cycle provide requisite insight into the methodology.

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

A new IrIII 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 H2 PO4 - and HP2 O7 3- in acetonitrile. An increase in the lifetime (τ) from 0.03543 µs to 0.2736 µs and 0.1323 µs in the presence of H2 PO4 - and HP2 O7 3- , respectively, among all other competitive anions establishes Ir-1 as a simple lifetime-based sensor. Furthermore, 13.7- and 8.5-fold enhancement in PL intensities of Ir-1 along with blue-shifting is seen with H2 PO4 - and HP2 O7 3- , respectively. High selectivity of Ir-1 for these two ions even in the presence of a large excess of other anions also displayed sensitive detection (LOD=0.035 µM for HP2 O7 3- and 0.040 µM for H2 PO4 - ). NMR data further suggest that the recognition of phosphates by Ir-1 is occurring through C-H⋅⋅⋅phosphate hydrogen bond (HB) interaction.

Section 5(2) MHA 1983: results of a three-year rapid cycle clinical audit.

The aim of this paper was to establish whether section 5(2) of the Mental Health Act 1983 was being used appropriately in an inpatient psychiatric unit in the UK. A clinical audit was conducted over three consecutive years. Peer review of decisions to use section 5(2) on the hospital's adult and old age wards was conducted by junior medical staff. Ninety-eight per cent of the uses of section 5(2) were felt to be appropriate and most were reviewed within 72 hours. Very few patients (5%) were placed on this section again during their admission. The number placed on section 5(4) prior to section 5(2) increased from 2% to 12%. The proportion reviewed within the first 24 hours of detention nearly doubled over the audit period and fewer patients subsequently went on to sections 2 or 3 by the third year. There was no evidence of inappropriate use of section 5(2). Changes in the shift system for junior medical staff may have inadvertently led to a more frequent use of section 5(4). The use of further formal detention after section 5(2) declined, although this decline was not statistically significant.