Emission, Raman spectroscopy, and structural characterization of actinide tetracyanometallates.

Three new compounds, {U2(H2O)10(O)[Pt(CN)4]3}·4H2O, {Th2(H2O)10(OH)2[Pd(CN)4]3}·8H2O, and {(UO2)2(DMSO)4(OH)2[Ni(CN)4]}, in the actinide tetracyanometallate, Anx[M(CN)4]y, class of compounds have been synthesized and characterized by confocal Raman spectroscopy and single crystal X-ray diffraction. These compounds contain unique structures illustrating dimeric actinide species. The absence of intense charge transfer emission in the visible range for {U2(H2O)10(O)[Pt(CN)4]3}·4H2O, as compared to the platinum starting material, is unusual because of the presence of pseudo-one-dimensional Pt···Pt chains in this compound. Confocal Raman spectroscopy of the cyanide stretching region provides insight into the binding domain (mono-, bi-, tri-, tetradentate) of the tetracyanometallates in these novel structures.

Coordination chemistry with f-element complexes for an improved understanding of factors that contribute to extraction selectivity.

Here, we highlight some recent accomplishments in f-element coordination chemistry aimed at probing the fundamental chemical differences between the 4f elements, lanthanides, and the 5f elements, actinides. The studies of particular interest are those that target improving our knowledge of fundamental chemistry to aid in increased selectivity for extractions of actinides. Two components key to understanding the challenges of actinide separations are detailed here, namely, previously described separation methods and recent investigations into the fundamental coordination chemistry of actinides. Both are aimed at probing the critical features necessary for improved selectivity of separations. This is considered a critical goal in the safe remediation of contaminated sites and reprocessing of nuclear fuel sources used in either civilian and noncivilian energy production.

Actinide tetracyanoplatinates: synthesis and structural characterization with uncharacteristic Th-NC coordination and thorium fluorescence.

Here, we report the synthesis of three novel actinide tetracyanoplatinates (AnTCP, where An = Th, UO(2) unit and TCP = [Pt(CN)(4)](2-)) along with their unique fluorescence properties and structural characterization by single crystal X-ray diffraction.

Emission enhancement through dual donor sensitization: modulation of structural and spectroscopic properties in a series of europium tetracyanoplatinates.

The synthesis of three different europium tetracyanoplatinates all incorporating 2,2':6',2''-terpyridine (terpy) have been carried out in acetonitrile/water mixtures by reaction of Eu(3+) salts with terpy and potassium tetracyanoplatinate. The use of different Eu(3+) sources results in the isolation of Eu(C(15)H(11)N(3))(H(2)O)(2)(NO(3))(Pt(CN)(4)) x CH(3)CN (1), {Eu(C(15)H(11)N(3))(H(2)O)(3)}(2)(Pt(CN)(4))(3) x 2 H(2)O (2), or [Eu(C(15)H(11)N(3))(H(2)O)(2)(CH(3)COO)(2)](2)Pt(CN)(4) x 3 H(2)O (3) for the nitrate, triflate, or acetate salts, respectively. All three compounds have been prepared as colorless crystals, and single-crystal X-ray diffraction has been used to investigate their structural features. Crystallographic data (MoK alpha, lambda = 0.71073 A, T = 290 K): 1, monoclinic, space group P2(1)/c, a = 12.835(1), b = 15.239(1), c = 13.751(2) A, beta = 105.594(9) degrees, V = 2590.8(5) A(3), Z = 4; 2, triclinic, space group P1, a = 9.1802(8) A, b = 10.8008(9) A, c = 13.5437(9) A, alpha = 84.491(6) degrees, beta = 75.063(7) degrees, gamma = 79.055(7) degrees, V = 1272.4(2) A(3), Z = 1; 3, triclinic, space group P1, a = 12.110(3) A, b = 12.7273(11) A, c = 18.7054(16) A, alpha = 92.859(7) degrees, beta = 92.200(11) degrees, gamma = 118.057(10) degrees, V = 2534.8(7) A(3), Z = 2. Variation of the counteranions in these systems provides the opportunity to modify the structures and coordination environment of Eu(3+) for 1-3. Compounds 1 and 2 are both one-dimensional, polymeric compounds that contain Eu(3+) ions chelated by terpy and bridged by tetracyanoplatinate anions. 3 is a zero-dimensional complex salt in which Eu(3+) is coordinated by terpy, acetate, and water, but not tetracyanoplatinate. The structural differences result in varying sensitization phenomena for the three compounds. Compounds 1 and 2 display efficient donor-acceptor intramolecular energy transfer (IET) where dual donor species, terpyridine and tetracyanoplatinate, simultaneously enhance the acceptor Eu(3+) emission. In both compounds the donor species are directly coordinated to the acceptor ion, and hence a highly efficient dual-donor effect is exhibited for the IET mechanisms. In 3 where only the terpy ligand is directly coordinated to Eu(3+), the sensitization involves only one donor species. The Pt(CN)(4)(2-) unit in 3, which lacks direct bonding to Eu(3+), exhibits strong emission indicating the lack of cooperative enhancement of the lanthanide emission.

catena-Poly[[[diaqua-(nitrato-κO,O')(2,2':6',2''-terpyridine-κN,N',N'')neodymium(III)]-µ-cyanido-κN:C-[dicyanidoplatinum(II)]-µ-cyanido-κC:N] acetonitrile solvate 2,2':6',2''-terpyridine hemisolvate].

The title compound, {[NdPt(CN)(4)(NO(3))(C(15)H(11)N(3))(H(2)O)(2)]·CH(3)CN·0.5C(15)H(11)N(3)}(n), was isolated from solution as a one-dimensional coordination polymer. The Nd(3+) site in the structure has a ninefold coordination with a distorted tricapped trigonal-prismatic geometry, while the Pt(II) ion is coordinated by four cyanide groups in an almost regular square-planar geometry. Cis-bridging by the tetracyanidoplatinate anions links the Nd(3+) cations, forming the one-dimensional chains. Additionally, each Nd(3+) contains coordin-ation by two water mol-ecules, one tridentate 2,2':6',2''-terpyridine mol-ecule, and one bidentate nitrate anion. 2,2':6',2''-Terpyridine and acetonitrile solvent mol-ecules are incorporated between the chains, the former form π-stacking inter-actions (average inter-planar distance 3.33 Å) with terpyridine mol-ecules located in the chains. Relatively long Pt⋯Pt inter-actions [3.847 (1) Å] are observed in the structure. O-H⋯N and O-H⋯O hydrogen bonding interactions between the consituents consolidates the crystal packing.

Intramolecular energy transfer in a one-dimensional europium tetracyanoplatinate.

The one-dimensional, polymeric compound (C15H11N3)Eu(H2O)2(NO3)(Pt(CN)4).CH3CN (1) has been shown to display an efficient donor-acceptor intramolecular energy-transfer (IET) process where ligand donors transfer energy to the Eu (III) acceptor. Single-crystal X-ray diffraction has been used to investigate the structural features of this compound in order to help understand the observed IET process. Crystallographic data: 1, monoclinic, space group P2(1)/c, a = 12.835(1) A, b = 15.239(1) A, c = 13.751(2) A, beta = 105.594(9) degrees , V = 2590.8(5) A(3), and Z = 4 (T = 290 K).

A nearly planar arrangement of ions in 4,4'-bipiperidinium tetra-cyanido-platinate(II) monohydrate.

The title compound, (C(10)H(22)N(2))[Pt(CN)(4)]·H(2)O, was isolated from solution as a mol-ecular salt. The compound contains discrete 4,4'-bipiperidinium cations and tetra-cyano-platinate(II) anions that are involved in a hydrogen-bonding network with one water mol-ecule of hydration. The structure differs from that of the similar acetonitrile solvate, (C(10)H(22)N(2))[Pt(CN)(4)]·2CH(3)CN, in the orientation of the ions relative to one another. The hydrate reported here contains layers of nearly parallel cations and anions with an angle between their mean planes of only 4.35 (11)°, while in the acetonitrile solvate the cations and anions are nearly perpendicular to one another (86.1° between mean planes). The crystal showed partial inversion twinning.