Cancellation of stark shifts in optical lattice clocks by use of pulsed Raman and electromagnetically induced transparency techniques

We propose a combination of electromagnetically induced transparency-Raman and pulsed spectroscopy techniques to accurately cancel frequency shifts arising from electromagnetically induced transparency fields in forbidden optical clock transitions of alkaline earth atoms. At appropriate detunings, time-separated laser pulses are designed to trap atoms in coherent superpositions while eliminating off-resonance ac Stark contributions, achieving efficient population transfer up to 60% with inaccuracy <10(-17). Results from the wave-function formalism are confirmed by the density matrix approach.     

Replacement of chlorides with dicarboxylate ligands in anticancer active Ru(II)-DMSO compounds: a new strategy that might lead to improved activity

A series of new Ru(II)-DMSO complexes containing dicarboxylate ligands (dicarb), namely, oxalate (ox), malonate (mal), methylmalonate (mmal), dimethylmalonate (dmmal), and succinate (suc), have been synthesized and structurally characterized. These compounds were prepared from the known Ru(II)-Cl-DMSO anticancer complexes cis,fac-[RuCl2(DMSO-S)3(DMSO-O)] (1) and trans-[RuCl2(DMSO-S)4] (2) and from the chloride-free precursor fac-[Ru(DMSO-S)3(DMSO-O)3][CF3SO3]2 (3), with the aim of assessing how the nature of the anionic ligands influences the biological activity of these species. Basically, the investigated ligands can be divided into two groups. The reaction of either 1 or 2 with K2(dicarb) (dicarb = ox, mal, mmal) yielded preferentially the mononuclear species [K]fac-[RuCl(DMSO-S)3(eta2-dicarb)] (dicarb = mal, 6; mmal, 9; ox, 14) that contains a chelating dicarboxylate unit and a residual chloride. Likewise, when 3 was used as a precursor, the neutral mononuclear species fac-[Ru(DMSO-O)(DMSO-S)3(eta2-dicarb)] (dicarb = mal, 7; mmal, 10; ox, 16), which contains a DMSO-O ligand in the place of Cl-, was obtained. On the contrary, K2(suc) and K2(dmmal) yielded preferentially the dinuclear species [fac-Ru(DMSO-S)3(H2O)(mu-dicarb)]2 (dicarb = dmmal, 11; suc, 13), with two bridging dicarboxylate moieties. The two water molecules in anti geometry have strong intramolecular H-bonding with the non-coordinated oxygen atoms of the carboxylate groups. The solid-state X-ray structural data showed that the preferential binding mode of the investigated dicarboxylates, either bridging (mu) or chelating (eta2), is dictated mainly by steric reasons. Oxalate, unlike the other dicarboxylates, has also the bridging bis-chelate (eta4,mu) coordination mode available: this was found in the dinuclear species [{fac-RuCl(DMSO-S)3}2(eta4,mu-ox)] (15) and [{fac-Ru(DMSO-O)(DMSO-S)3}2(eta4,mu-ox)][CF3SO3]2 (17). We also isolated the unprecedented neutral metallacycle, [fac-Ru(DMSO-S)3(eta3,mu-ox)]4 (18), in which each oxalate unit has one unbound oxygen atom. The new complexes were thoroughly characterized by 1-D (1H and 13C) and 2-D (H-H- COSY and HMQC) NMR spectroscopy in solution and by IR spectroscopy in the solid state. The molecular structures of 10 compounds, 6-11, 13, 15, 17, and 18, were determined by X-ray crystallography. The behavior of selected complexes in aqueous solution was investigated by 1H NMR spectroscopy.     

Self-assembled metallacycles with pyrazine edges: a new example in which the unexpected molecular triangle prevails over the expected molecular square

The combination of cis-protected metal fragments with linear linkers is expected to yield molecular squares. We found instead that treatment of the 90 degrees angular precursor trans-[RuCl2(dmso-S)4] (1) with an equivalent amount of the linear and rigid pyrazine (pyz) linker unexpectedly yields, in a number of different experimental conditions, the molecular triangle [{trans,cis-RuCl2(dmso-S)2(mu-pyz)}3] (3), together with polymeric material. Very similar results were also obtained from the reaction between 1 and the preformed corner fragment trans,cis,cis-[RuCl2(dmso-S)2(pyz)2] (6). In both cases, the expected molecular square [{trans,cis-RuCl2(dmso-S)2(mu-pyz)}4] (4) was observed only as a transient species. These results suggest that 3, which is the first example of a neutral molecular triangle with octahedral metal corners and pyrazine edges, is both the thermodynamic and the kinetic product of the reactions described above. The X-ray structure of 3 shows that the main distortions from ideal coordination geometry concern the N-Ru-N angles, which are narrower than 90 degrees , and the coordination bonds of pyz. The pyrazine molecules, which are basically planar, are significantly tilted from linearity. Calculations performed on 6 indicated that the N-Ru-N angle is ca. six times more rigid than the tilt angle of pyrazine. The structural and theoretical findings on 3 and 6, together with the previous examples of molecular triangles and squares with cis-protected metal corners and linear pyz edges, suggest that the entropically favored molecular triangles might be preferred over the expected molecular squares with metal corner fragments that spontaneously favor Npyz-M-Npyz angles narrower than 90 degrees because of the presence of ancillary ligands with significant steric demand on the coordination plane. The rather-flexible coordination geometry of pyrazine can accommodate the moderate distortions from linearity required to close the small metallacycle with modest additional strain.     

3D Heterometallic (3d–4f) coordination polymers: A ferromagnetic interaction in a Gd(III)–Cu(II) couple

Four 3d–4f heterometallic coordination polymers, [Cu₃(IDA)₆Ln₂] · n(H₂O) [IDA =  iminodiacetate dianion; Ln = Gd, n = 3 (1); Ln = Nd, n = 6 (2); Ln = Sm, n = 6 (3)] and [Cu(Cl)(NTA)Sm(H₂O)₆] · (ClO₄) · (H₂O) (4) [NTA = nitrilotriacetate trianion], have heen synthesized and characterized by single crystal X-ray diffraction analysis. Complexes 1–3 are isomorphous, showing a 3D coordination framework having tubular channels filled by lattice water molecules running parallel to the c axis. Whereas complex 4 is a 1D polymer of alternating copper and samarium ions connected by NTA, and the chains get involved in H-bonding interactions resulting in a 3D network. A low temperature magnetic study reveals ferromagnetic interactions for complex 1. Thermogravimetric and X-ray powder diffraction analyses of 1, 2 and 3 show that the covalently bonded 3D network remains almost unaffected after deaquation.     

124I Radiolabeling of a AuIII-NHC Complex for In Vivo Biodistribution Studies

Au^III complexes with N-heterocyclic carbene (NHC) ligands have shown remarkable potential as anticancer agents, yet their fate in vivo has not been thoroughly examined and understood. Reported herein is the synthesis of new Au^III-NHC complexes by direct oxidation with radioactive [¹²⁴I]I₂ as a valuable strategy to monitor the in vivo biodistribution of this class of compounds using positron emission tomography (PET). While in vitro analyses provide direct evidence for the importance of Au^III-to-Au^I reduction to achieve full anticancer activity, in vivo studies reveal that a fraction of the Au^III-NHC prodrug is not immediately reduced after administration but able to reach the major organs before metabolic activation.     

Syntheses, crystal structures, and magnetic properties of [Ln(III)2(Succinate)3(H2O)2].0.5H2O [Ln = Pr, Nd, Sm, Eu, Gd, and Dy] polymeric networks: unusual ferromagnetic coupling in Gd derivative

Lanthanide-organic coordination polymeric networks of [Ln(III)2(suc)3(H2O)2].0.5H2O [suc = succinate dianion, Ln = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), and Dy (6)] have been synthesized and characterized by single-crystal X-ray diffraction analyses. The structural determination reveals that complexes are isomorphous, all crystallizing in monoclinic system, space group I2/a(.) The complexes possess a 3D architecture with Ln ion in a nine-coordination geometry attained by eight oxygen atoms from succinate and one oxygen atom from an aqua ligand. Low-temperature magnetic study indicates that ferromagnetic interaction is present in case of Gd(III) and Dy(III). Antiferromagnetic interaction is observed for the rest of the complexes. Density functional theory calculations are performed which support the existence of a superexchange ferromagnetic coupling in Gd(III) ions, whereas classical crystal field model has been applied to study the complexes 1, 2, 3, and 6.