Generation of multimillion chemical space based on the parallel Groebke-Blackburn-Bienaymé reaction.

Parallel Groebke-Blackburn-Bienaymé reaction was evaluated as a source of multimillion chemically accessible chemical space. Two most popular classical protocols involving the use of Sc(OTf) and TsOH as the catalysts were tested on a broad substrate scope, and prevalence of the first method was clearly demonstrated. Furthermore, the scope and limitations of the procedure were established.

Spectroscopic and Theoretical Insights into Surprisingly Effective Sm(III) Extraction from Alkaline Aqueous Media by -Phenylenediamine-Derived Sulfonamides.

Alkaline high-level waste (HLW) generated as a result of years of nuclear weapons production has complicated composition and requires comprehensive treatment methods, which would allow concentrating its most radiotoxic components in a small volume for geological disposal. We have investigated six alkyl-substituted -phenylenediamine-derived sulfonamides for extraction and consecutive stripping of Sm(III) from alkaline aqueous media. Up to 81% of Sm(III) recovery at pH 13.

Coordination polymers of Cd and Pb with croconate show remarkable differences in coordination patterns: a structural and spectroscopic study.

The croconate dianion is a highly versatile ligand with two tautomeric forms making it useful for building large superstructures in the solid state. The single-crystal X-ray structures of Pb- and Cd-croconate coordination polymers, namely catena-poly[[[diaqualead(II)]-μ-croconato-κO,O:O,O] monohydrate], {[Pb(CO)(HO)]·HO}, 1, and catena-poly[[triaquacadmium(II)]-μ-croconato-κO,O:O,O], [Cd(CO)(HO)], 2, have been determined. Both polymers form one-dimensional (1D) structures; 1 is a nonplanar 1D zigzag coordination polymer extended along the crystallographic b axis, whereas 2 is a planar 1D ribbon parallel to the [101] direction.

A Redox-Induced Spin-State Cascade in a Mixed-Valent Fe (μ -O) Triangle.

One-electron reduction of a pyrazolate-bridged triangular Fe (μ -O) core induces a cascade wherein all three metal centers switch from high-spin Fe to low-spin Fe . This hypothesis is supported by spectroscopic data ( H-NMR, UV-vis-NIR, infra-red, Fe-Mössbauer, EPR), X-ray crystallographic characterization of the cluster in both oxidation states and also density functional theory. The reduction induces substantial contraction in all bond lengths around the metal centers, along with diagnostic shifts in the spectroscopic parameters.

Double exchange in a mixed-valent octanuclear iron cluster, [Fe8(μ4-O)4(μ-4-Cl-pz)12Cl4](-).

A combination of SQUID and pulsed high-field magnetometry is used to probe the nature of mixed valency in an Fe(II)Fe7(III) cluster. DFT-computed spin Hamiltonian parameters suggest that antiferromagnetic coupling dominates, and that electron transfer both between the four irons of the cubane core (t1) and between a cubane and three neighboring irons (t2) is significant. Simulations using the computed parameters are able to reproduce the key features of the measured effective magnetic moment, μeff(T), over the 2 < T < 300 K temperature range.

Self-assembly hexanuclear metallacontainer hosting halogenated guest species and sustaining structure of 3D coordination framework.

Chloride-centered hexanuclear hydroxopyrazolate reveals potential as a receptor of halomethane and halometallate species and as a molecular building block for coordination polymers.

Zinc(II) and cadmium(II) chloride complexes with 4,4'-bi-1,2,4-triazole.

New coordination compounds with the 4,4'-bi-1,2,4-triazole ligand (btr), namely tetraaqua-2kappa(4)O-di-mu(2)-4,4'-bi-1,2,4-triazole-1:2kappa(2)N(1):N(1');2:3kappa(2)N(1):N(1')-hexachlorido-1kappa(3)Cl,3kappa(3)Cl-trizinc(II), [Zn(3)Cl(6)(C(4)H(4)N(6))(2)(H(2)O)(4)], (I), and poly[cadmium(II)-mu(2)-4,4'-bi-1,2,4-triazole-kappa(2)N(1):N(2)-di-mu(2)-chlorido], [CdCl(2)(C(4)H(4)N(6))](n), (II), reveal an unprecedented molecular zwitterionic structure for (I) and a polymeric two-dimensional layer structure for (II). Differences between these products, which involve the formation of either charge-separated chlorometallate/aquametal fragments or complementary organic and inorganic bridges, are attributable to the hardness-softness characters of the metal cations. In (I), two N(1),N(1')-bidentate btr molecules connect one [Zn(H(2)O)(4)](2+) cation and two [ZnCl(3)](-) anions into a linear trizinc motif (the Zn atom of the cation occupies a centre of inversion in an N(2)O(4) coordination octahedron, whereas the Zn atom of the anion possesses a distorted tetrahedral Cl(3)N environment).

Metal-organic frameworks incorporating Cu3(mu3-OH) clusters.

Interaction of 4,4-bi(1,2,4-triazole) (btr) with copper(II) chloride (bromide) in aqueous or aqueous alcohol media led to a series of coordination polymers featuring the formation of mu 3-hydroxotricopper(II) clusters and their integration into 3D frameworks. These unprecedented structures originate in the propagation of trigonal hydroxotricopper(II) clusters bridged by tri- or tetradentate organic ligands. Complex [{Cu3(mu3-OH)}{Cu3(mu3-O)}(mu4-btr)3(H2O)4(OH)2Cl6]Cl.