Analysis of Random Lasing in Human Blood.

Random lasing (RL) is an optical phenomenon that arises from the combination of light amplification with optical feedback through multiple scattering events. In this paper, we present our investigations of RL generation from human blood samples. We tested mixtures of rhodamine B dye solutions with different blood components, including platelets, lymphocytes, erythrocytes, and whole blood.

Stereocontrol of Metal-Centred Chirality in Rhodium(III) and Ruthenium(II) Complexes with NN'P Ligand.

Rh(III) and Ru(II) complexes, [RhCl(κ-NN'P-L)][SbF] (1) and [RuCl(κ-NN'P-L)] (2), were synthesised using the tetradentate ligand L (L=N,N-bis[(pyridin-2-yl)methyl]-[2-(diphenylphosphino)phenyl]methanamine). In each case only one diastereomer is detected, featuring cis-disposed pyridine groups. The chloride ligand trans to pyridine can be selectively abstracted by AgSbF, with the ruthenium complex (2) reacting more readily at room temperature compared to the rhodium complex (1) which requires elevated temperatures.

Molecular Dihydrogen Activation by (CMe)M/N (M=Rh, Ir) Transition Metal Frustrated Lewis Pairs: Reversible Proton Migration to, and Proton Abstraction from, the CMe Ligand.

The masked transition-metal frustrated Lewis pairs [Cp*M(κN,N',N''-L)][SbF] (Cp*=η-CMe; M=Ir, 1, Rh, 2; HL=pyridinyl-amidine ligand) reversibly activate H under mild conditions rendering the hydrido derivatives [Cp*MH(κN,N'-HL)][SbF] observed as a mixture of the E and Z isomers at the amidine C=N bond (M=Ir, 3Z, 3E; M=Rh, 4Z, 4E). DFT calculations indicate that the formation of the E isomers follows a Grotthuss type mechanism in the presence of water. A mixture of Rh(I) isomers of formula [(Cp*H)Rh(κN,N'-HL)][SbF] (5 a-d) is obtained by reductive elimination of Cp*H from 4.

Dynamic Configuration on a Chiral-at-Rhodium Catalyst Featuring a Flexible Tetradentate Ligand.

The unique dynamic configuration of an enantioselective chiral-at-metal catalyst based on Rh(III) and a non-chiral tetradentate ligand is described and resolved. At room temperature, the catalyst undergoes a dynamic configuration process leading to the formation of two interconvertible metal-stereoisomers, remarkably without racemization. Density functional theory (DFT) calculations indicate that this metal-isomerization proceeds via a concerted transition state, which features a trigonal bipyramidal geometry stabilized by the tetradentate ligand.

Molecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays.

The transition metal frustrated Lewis pair compounds [(Cym)M(κS,P,N-HL1)][SbF] (Cym = η--MeCHiPr; H2L1 = -(-tolyl)-'-(2-diphenylphosphanoethyl)thiourea; M = Ru (5), Os (6)) have been prepared from the corresponding dimer [{(Cym)MCl}(μ-Cl)] and H2L1 by successive chloride abstraction with NaSbF and AgSbF and NH deprotonation with NaHCO. Complexes 5 and 6 and the previously reported phosphano-guanidino compounds [(Cym)M(κP,N,N'-HL2)][SbF] [H2L2 = ,'-bis(-tolyl)-''-(2-diphenylphosphanoethyl) guanidine; M = Ru (7), Os (8)] and pyridinyl-guanidino compounds [(Cym)M(κN,N',N''-HL3)][SbF] [H2L3 = ,'-bis(-tolyl)-''-(2-pyridinylmethyl) guanidine; M = Ru (9), Os (10)] heterolytically activate H in a reversible manner affording the hydrido complexes [(Cym)MH(H2L)][SbF] (H2L = H2L1; M = Ru (11), Os (12); H2L = H2L2; M = Ru (13), Os (14); H2L = H2L3; M = Ru (15), Os (16)). DFT calculations carried out on the hydrogenation of complex 7 support an FLP mechanism for the process.