Hexanuclear Complex Research Articles

Hexanuclear copper(II) complex of 2-hy-droxy-N,N'-bis-[1-(2-hy-droxy-phen-yl)ethyl-idene]propane-1,3-di-amine incorporating an open-cubane core.

The title mol-ecular structure, namely, di-aqua-tris-(μ3-1,3-bis-{[1-(2-oxidophen-yl)ethyl-idene]amino}-propan-2-olato)-μ3-hydroxido-dinitrato-hexa-copper(II) ethanol tris-olvate, [Cu6(C19H19N2O3)3(NO3)2(OH)(H2O)2]·3C2H5OH, corres-ponds to a non-symmetric hexa-nuclear copper complex. The complex exhibits one core in which three CuII metal centres are mutually inter-connected, two by two, via three phenolato oxygen anions acting in a μ2-mode. These three copper cations are inter-connected in a μ3-mode by one hydroxyl group. An open-cube structure is generated in which each of the CuII cations of the three CuO4N units is connected by two μ2-O anions from phenolate groups and one μ3-O atom from a hy-droxy anion. Each of the three penta-coordinated CuII cations situated in the open-cube unit has a distorted NO4 square-pyramidal environment. Each of these three CuII centres is inter-connected with another CuII cation via one enolate O atom in μ2-mode, yielding one CuNO4 unit and two CuNO3 units. The penta-coordinated CuII atom has a distorted square-pyramidal environment while the two tetra-coordinated copper(II) cations are situated in a square-planar environment. A series of intra-molecular O-H⋯O hydrogen bonds are observed. In the crystal, the units are connected two by two by inter-molecular C-H⋯O and O-H⋯O hydrogen bonds, thus forming sheets parallel to the ac plane.

Thermodynamic and solubilization properties of a polynuclear copper complex in ionic surfactants media

The solubilization behavior of hexanuclear copper complex, [Cu6(η1 :μ2 -C4H10NO)4(η1 :η1 :μ2 -C5H9O2)4(η1 :μ1 -C5H9O2)2(μ 3-OH)2] (1) (where, C4H10NO = N,N-dimethylethanolamine and C5H9O2 = pivalic acid) ionic micellar media has been explored in this study. The interaction of copper cluster under investigation (1) was experimented with an anionic surfactant (sodium lauryl sulfate; SLS) and a cationic surfactant (cetyltrimethyl ammonium bromide; CTAB). Solubilization was observed in aqueous solutions of ionic surfactants at their pre-micellar, micellar and post-micellar concentrations ranges using UV–Visible spectroscopy and electrical conductivity. The thermodynamic attributes of micellization including standard entropy (ΔSmic ), enthalpy (ΔHmic ) and free energy (ΔGmic ) were estimated from electrical conductivity measurements. The negative values of ΔGmic and ΔHmic indicated the stability of micellization, in addition to the enthalpy and entropy-driven nature of the process. Thermodynamic studies demonstrate increases in the CMC of both surfactants due to incorporation of the copper complex in the micelles. Partitioning and binding parameters were revealed by UV–Vis spectroscopy to quantitatively measure the interaction of the copper cluster with the surfactant in terms of partition constant (Kc ), partition coefficient (Kx ), binding coefficient (Kbind ), and free energies of free energy of partition (ΔGpart ) and binding (ΔGbind ). The presence of cationic CTAB led to greater red-shift in UV–Vis study of 1 as compared to SLS due to stronger ionic interactions. The strong interaction and high solubility have been seen in 1 with CTAB as compared to SLS.

Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle.

Spherical assemblies of the type [Pdn L2n ]2n+ can be obtained from PdII salts and curved N-donor ligands, L. It is well established that the bent angle, α, of the ligand is a decisive factor in the self-assembly process, with larger angles leading to complexes with a higher nuclearity, n. Herein, we report heteroleptic coordination cages of the type [Pdn Ln L'n ]2n+ , for which a similar correlation between the ligand bent angle and the nuclearity is observed. Tetranuclear cages were obtained by combining [Pd(CH3 CN)4 ](BF4 )2 with 1,3-di(pyridin-3-yl)benzene and ligands featuring a bent angle of α=120°. The use of a dipyridyl ligand with α=149° led to the formation of a hexanuclear complex with a trigonal prismatic geometry; for linear ligands, octanuclear assemblies of the type [Pd8 L8 L'8 ]16+ were obtained. The predictable formation of heteroleptic PdII cages from 1,3-di(pyridin-3-yl)benzene and different dipyridyl ligands is evidence that there are entire classes of heteroleptic cage structures that are privileged from a thermodynamic point of view.

Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives.

Two novel copper(II) complexes of formulas {[Cu(4-Hmpz)4][Cu(4-Hmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(ClO4)2]}n (1) and {[Cu(3,4,5-Htmpz)4]2[Cu(3,4,5-Htmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(H2O)(ClO4)]2[Cu2(3,4,5-Htmpz)4(µ-ox-κ2O1,O2:κ2O2′,O1′)]}(ClO4)4·6H2O (2) have been obtained by using 4-methyl-1H-pyrazole (4-Hmpz) and 3,4,5-trimethyl-1H-pyrazole (3,4,5-Htmpz) as terminal ligands and oxalate (ox) as the polyatomic inverse coordination center. The crystal structure of 1 consists of perchlorate counteranions and cationic copper(II) chains with alternating bis(pyrazole)(µ3-κ2O1,O2:κO2′:κO1′-oxalato)copper(II) and tetrakis(pyrazole)copper(II) fragments. The crystal structure of 2 is made up of perchlorate counteranions and cationic centrosymmetric hexanuclear complexes where an inner tetrakis(pyrazole)(µ-κ2O1,O2:κ2O2′,O1′-oxalato)dicopper(II) entity and two outer mononuclear tetrakis(pyrazole)copper(II) units are linked through two mononuclear aquabis(pyrazole)(µ3-κ2O1,O2:κO2′:κO1′-oxalato)copper(II) units. The magnetic properties of 1 and 2 were investigated in the temperature range 2.0–300 K. Very weak intrachain antiferromagnetic interactions between the copper(II) ions through the µ3-ox-κ2O1,O2:κO2′:κO1′ center occur in 1 [J = −0.42(1) cm−1, the spin Hamiltonian being defined as H = −J∑S1,i · S2,i+1], whereas very weak intramolecular ferromagnetic [J = +0.28(2) cm−1] and strong antiferromagnetic [J’ = −348(2) cm−1] couplings coexist in 2 which are mediated by the µ3-ox-κ2O1,O2:κO2′:κO1′ and µ-ox-κ2O1,O2:κ2O2′,O1′ centers, respectively. The variation in the nature and magnitude of the magnetic coupling for this pair of oxalato-centered inverse copper(II) complexes is discussed in the light of their different structural features, and a comparison with related oxalato-centered inverse copper(II)-pyrazole systems from the literature is carried out.

Assembly of Heterometallic AuICu2I2 Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine.

The row of metallocyclic dinuclear gold(I) complexes with cyclic diphosphines, namely, P-pyridylethyl-substituted 1,5-diaza-3,7-diphosphacyclooctanes, has been obtained. Further interaction of the dinuclear gold(I) complexes with copper(I) iodide gave the first examples of hexanuclear AuI/CuI complexes containing two unusual trinuclear AuICu2I2 fragments. The structures of di- and hexanuclear complexes were confirmed by NMR spectroscopy, ESI mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. All of the obtained complexes are moderate emitters in the solid state. Dinuclear gold(I) complexes displayed a greenish emission with the maxima in the emission spectra at ca. 550 nm. The obtained hexanuclear heterobimetallic AuI/CuI complexes are triplet solid-state blue emitters with the maximum in the emission spectra at 463 and 484 nm. According to the TD-DFT calculations, the observed emission of all studied complexes had a triplet origin and was caused by the 3CC or 3(MLCT) T1 → S0 transitions for dinuclear and hexanuclear complexes, respectively.

Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates.

Reaction of 2,2′-bipyridine (2,2′-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)2(EtOH)]n led to the formation of binuclear complexes [Mn2(Piv)4L2] (L = 2,2′-bipy (1), phen (2); Piv− is the anion of pivalic acid). Oxidation of 1 or 2 by air oxygen resulted in the formation of tetranuclear MnII/III complexes [Mn4O2(Piv)6L2] (L = 2,2′-bipy (3), phen (4)). The hexanuclear complex [Mn6(OH)2(Piv)10(pym)4] (5) was formed in the reaction of [Mn(Piv)2(EtOH)]n with pyrimidine (pym), while oxidation of 5 produced the coordination polymer [Mn6O2(Piv)10(pym)2]n (6). Use of pyrazine (pz) instead of pyrimidine led to the 2D-coordination polymer [Mn4(OH)(Piv)7(µ2-pz)2]n (7). Interaction of [Mn(Piv)2(EtOH)]n with FeCl3 resulted in the formation of the hexanuclear complex [MnII4FeIII2O2(Piv)10(MeCN)2(HPiv)2] (8). The reactions of [MnFe2O(OAc)6(H2O)3] with 4,4′-bipyridine (4,4′-bipy) or trans-1,2-(4-pyridyl)ethylene (bpe) led to the formation of 1D-polymers [MnFe2O(OAc)6L2]n·2nDMF, where L = 4,4′-bipy (9·2DMF), bpe (10·2DMF) and [MnFe2O(OAc)6(bpe)(DMF)]n·3.5nDMF (11·3.5DMF). All complexes were characterized by single-crystal X-ray diffraction. Desolvation of 11·3.5DMF led to a collapse of the porous crystal lattice that was confirmed by PXRD and N2 sorption measurements, while alcohol adsorption led to porous structure restoration. Weak antiferromagnetic exchange was found in the case of binuclear MnII complexes (JMn-Mn = −1.03 cm−1 for 1 and 2). According to magnetic data analysis (JMn-Mn = −(2.69 ÷ 0.42) cm−1) and DFT calculations (JMn-Mn = −(6.9 ÷ 0.9) cm−1) weak antiferromagnetic coupling between MnII ions also occurred in the tetranuclear {Mn4(OH)(Piv)7} unit of the 2D polymer 7. In contrast, strong antiferromagnetic coupling was found in oxo-bridged trinuclear fragment {MnFe2O(OAc)6} in 11·3.5DMF (JFe-Fe = −57.8 cm−1, JFe-Mn = −20.12 cm−1).

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters.

Three new titanium oxo-clusters Ti4O2(OiPr)10(OOCPhMe)2 (I), Ti6O4(OEt)8(OOCPhMe)8 (II) and Ti6O6(OEt)6(OOCCHPh2)6 (III) were obtained by easy one-step solvothermal reactions of titanium(iv) isopropoxide, alcohols and carboxylic acids. The three compounds were characterized by single-crystal and powder X-ray diffraction, TGA/DSC, optical and electron microscopy, and FTIR and NMR spectroscopy. X-ray powder diffraction and spectroscopy confirmed the purity of the compounds. Structural analysis indicates that in all compounds the titanium(iv) ions are six-coordinated (distorted octahedra). (I) is a tetranuclear complex containing a Ti4(μ4-O)(μ2-O) core, which is linked by two (μ2-OOCPhMe), four (μ2-OiPr) and six OiPr ligands. (II) and (III) are hexanuclear complexes with different cores, respectively Ti6(μ3-O)2(μ2-O)2 and Ti6(μ3-O)6. The coordination sphere of the Ti atoms is filled by eight (μ2-OOCPhMe), two (μ2-OEt) and six OEt in (II) and six (μ2-OOCHPh2) and six OEt in (III). Different steric hindrance of substituents attached to the carboxyl group or different concentrations lead to three main different cluster geometries with two ligands. The tetranuclear and the hexanuclear clusters were obtained with the OOCPhMe ligand, while the hexagonal prism cluster was obtained with the OOCCHPh2 ligand. Hirshfeld surface calculations indicated that the packing is driven by C–O⋯H–C weak hydrogen bonds. The clusters can be used as molecular models of organic molecules bonded to titania surface, used in organic photovoltaic (dye sensitized solar cells) or other optoelectronic applications.

Speciation and separation of platinum(iv) polynuclear complexes in concentrated nitric acid solutions.

Understanding the solution chemistry of Pt(iv) is crucial for the hydrometallurgy of precious metals. To gain such an understanding, the speciation and separation of Pt(iv) complexes in concentrated HNO3 solutions were investigated via Pt LIII edge X-ray absorption fine structure (XAFS) spectroscopy. The XAFS results for concentrated HNO3 solutions of Na2Pt(OH)6 revealed the dominant presence of Pt polynuclear complexes, wherein the formation of Pt(iv) polynuclear complexes depended on the metal concentration and the Na2Pt(OH)6 dissolution temperature. The dominant species present in a heated nitrate solution of 0.90 g-Pt L-1 and a non-heated nitrate solution of 3.2 g-Pt L-1 were dinuclear Pt(iv) complexes, whereas those in a heated solution of 3.0 g-Pt L-1 were predominantly larger polynuclear complexes, such as, tetra- and hexa-nuclear complexes. The presence of larger Pt(iv) complexes was confirmed via XAFS spectroscopy, wherein the adsorption of Pt(iv) ions from a 10 M HNO3 solution by a chelating resin functionalised with iminodiacetic acid and a strongly basic anion-exchange resin bearing trimethyl ammonium nitrate was examined. The adsorption of 50 mg L-1 of Pt(iv) by the two resins was tested using aqueous solutions diluted from heated HNO3 solutions with varying metal concentrations, and also from a non-heated solution. We found that Pt(iv) complexes from heating solutions containing high Pt(iv) concentrations displayed high adsorption percentages. In addition, the selective adsorption of Pt(iv) over Pd(ii), Ag(i), Cu(ii), Ni(ii), and Fe(iii) from a 10 M HNO3 solution was achieved using a strongly basic anion-exchange resin.

Spectroscopic evidence of chirality in tetranuclear Cu(II)-Schiff base complexes, catalytic potential for oxidative kinetic resolution of racemic benzoin

Two chiral Schiff base ligands 2-((1-hydroxy-3-phenylpropan-2-ylimino)methyl)-6-methoxyphenol (L1H2 ) and 2-(4-hydroxy-3-isopropylbut-1-enyl)-6-methoxyphenol (L2H2 ) have been synthesized by the condensation of l-phenylalaninol/l-valinol and o-vanillin (2-hydroxy-3-methoxy benzaldehyde). A tetranuclear homometallic Cu(II) complex [Cu4(L1H)2(L1)2] (ClO4)2 (C1) and a hexanuclear heterometallic complex [Cu4(L2)4Na2(DMF)2(H2O)] (ClO4)2 (C2) have been synthesized with the ligands. Both the complexes possess cubane like Cu4O4 core with interesting structural variations and inherit the chirality of their corresponding ligands. The catalytic potential of the complexes has been explored for the oxidative kinetic resolution of racemic benzoin. The electronic, optical and chiroptical properties of the ligands and the complexes have been studied by DFT and TD-DFT calculations.

Secondary Metal Coordination Using a Tetranuclear Complex as Ligand Leading to Hexanuclear Complexes with Enhanced Thermal Barriers for Electron Transfer

Postsynthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2(BPh4)2·6MeCN·H2O [1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyridin...

Triosmium Carbonyl Clusters Containing a Mixture of Dppm and Dppe Ligands

Four osmium carbonyl complexes were synthesized via microwave heating by reacting either Os3(CO)12 or Os3(CO)10( $$\mu$$ -dppm) with dppe, where dppm = bis(diphenylphosphino)methane and dppe = 1,2-bis(diphenylphosphino)ethane. Two of the complexes, Os3(µ-dppe)(CO)8(dppe) (1) and Os3(µ-dppm)(CO)8(dppe) (2), are the first examples of triangular triosmium clusters containing diphosphane ligands that exhibit both bridging and chelating coordination modes in the same molecule. Complexes 2 and [Os3(µ-dppm)(CO)9]2(µ-dppe) (3) are the first examples of triosmium clusters containing two different diphosphane ligands in the same molecule. Complexes 3 and [Os3(µ-dppe)(CO)9]2(µ-dppe) (4) are hexanuclear clusters containing two triangular Os3 units linked together by a bridging diphosphane ligand. Crystal structures for complexes 1–3 are reported. Two trinuclear cluster complexes, Os3(μ-dppe)(CO)8(dppe) (1) and Os3(μ-dppm)(CO)8(dppe) (2), and two hexanuclear cluster complexes, [Os3(μ-dppm)(CO)9]2(μ-dppe) (3) and [Os3(μ-dppe)(CO)9]2(μ-dppe) (4), were synthesized and characterized by X-ray crystal diffraction. Complexes 2 and 3 are the first examples of triangular triosmium clusters containing two different diphosphane ligands in the same molecule.

Synthesis and combustion inhibition efficiency of iron short-chain perfluorocarboxylates

This study reports an experimental exploration of the combustion inhibition efficiency of iron short-chain perfluorocarboxylates, namely, iron trifluoroacetate (FeTFA) and iron pentafluoropropionate (FePFP). The aim is to develop a new phosphor-free fire-extinguishing agent. The synthesized FeTFA and FePFP were characterized by ultraviolet–visible spectroscopy, Fourier-transform infrared spectroscopy, X-ray fluorescence measurements, and fast-atom bombardment mass spectrometry. The FeTFA and FePFP ligands (i) coordinate with the iron ions in bridging form via carboxylate oxygens, (ii) contain no Cl−, and (iii) are hexanuclear complexes with chemical formulas of C18F27O22Fe6 and C27F45O22Fe6, respectively. Suppression trials and thermogravimetric measurements revealed that (i) both FeTFA and FePFP have higher combustion inhibition ability at lower suppressant concentrations than ammonium dihydrogen phosphate (an active component in conventional fire-extinguishing agents), (ii) FePFP is remarkably more inhibition-efficient than FeTFA, and (iii) neither FeTFA nor FePFP hinder cellulose pyrolysis and char combustion in the condensed phase. Thermogravimetry–mass spectrometry measurements confirmed that (i) the main gas-phase decomposition product of FeTFA and FePFP is CF3, and (ii) FePFP is a better CF3 generator than FeTFA. The different inhibition abilities of the two complexes were attributed to their different CF3 generation abilities and eases of decomposing the complex.

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

AbstractThe reaction of Na[CoIII(d‐ebp)] (d‐H4ebp = N,N′‐ethylenebis[d‐penicillamine]) with [(AuICl)2(dppe)] (dppe = 1,2‐bis[diphenylphosphino]ethane) gave a cationic AuI4CoIII2 hexanuclear complex, [CoIII2(LAu4)]2+ ([1]2+), where [LAu4]4− is a cyclic tetragold(I) metalloligand with a 32‐membered ring, [AuI4(dppe)2(d‐ebp)2]4−. Complex [1]2+ crystallized with NO3− to produce a charge‐separation (CS)‐type ionic solid of [1](NO3)2. In [1](NO3)2, the complex cations are assembled to form cationic supramolecular hexamers of {[1]2+}6, which are closely packed in a face‐centered cubic (fcc) lattice structure. The nitrate anions of [1](NO3)2 were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO3−}4 and {NO3−}6, respectively. An analogous CS‐type ionic solid formulated as [NiIICoIII(LAu4)](NO3) ([2](NO3)) was obtained when a 1:1 mixture of Na[CoIII(d‐ebp)] and [NiII(d‐H2ebp)] was reacted with [(AuICl)2(dppe)], accompanied by the conversion of the diamagnetic, square‐planar [NiII(d‐H2ebp)] to the paramagnetic, octahedral [NiII(d‐ebp)]2−. While the overall fcc structure in [2](NO3) was similar to that of [1](NO3)2, none of the nitrate anions were accommodated in any hydrophobic tetrahedral interstice, reflecting the difference in the complex charges between [1]2+ and [2]+.

Structures and magnetic properties of two hexanuclear [Co2Ln4]complexes

The utilization of a Schiff-base ligand (E)-1-(((2-(hydroxymethyl)phenyl)imino)methyl)nap- hthalen-2-ol afforded two 3d-4f hexanuclear complexes of formula [CoIII2LnIII4(μ3-OH)2(NO3)4 (OAc)4L4(DMF)2]·2C2H5OH [Ln = Dy(1), Gd(2)]. Single-crystal X-ray diffffraction analysis revealed that complexes 1 and 2 were isomorphous and had a chair-like topology. The core was composed of a defect-dicubane Ln4 moiety, which were supported by two μ3-OH groups. Two CoIII ions flanked the Ln4 core with one positioned above and one below the Ln4 plane. Magnetic susceptibility measurements were performed for complexes 1 and 2. Complex 1 displays an out-of-phase signal in the alternating current susceptibility indicating slow magnetic relaxation behavior.

Charge-Separation-Type Ionic Crystals with Mixed AuI4CoIII2 and AuI4NiIICoIII Hexanuclear Complexes.

Treatment of a digold(I) metalloligand, [AuI2(dppe)(d-Hpen)2] (H2LAu; d-H2pen = d-penicillamine, dppe = 1,2-bis(diphenylphosphino)ethane), with a 1:1 mixture of Co(OAc)2 and Ni(OAc)2 under aerobic conditions resulted in the formation of three types of hexanuclear complexes: [CoIII2(LAu)2]2+, [NiIICoIII(LAu)2]+, and [NiII2(LAu)2]. The addition of NaNO3, M1NO3 (M1 = K, Rb, Cs), and M2(NO3)2 (M2 = Ca, Sr, Ba) to the reaction mixture led to co-crystallization of [CoIII2(LAu)2]2+ and [NiIICoIII(LAu)2]+ as a solid solution to form the charge-separation (CS)-type ionic crystals 1Na, 1M1, and 1M2, respectively, while [NiII2(LAu)2] independently crystallized as a single species (2). In 1Na, [CoIII2(LAu)2]2+ and [NiIICoIII(LAu)2]+ cations assemble in a 1:2 ratio to form a cationic supramolecular octahedron accommodating 4 H3O+ ions, while 10 nitrate ions are packed in each hydrophilic tetrahedral interstice of the crystal to form an anionic adamantane cluster. The overall structures of 1M1 and 1M2 are very similar to that of 1Na, having a CS-type structure composed of cationic supramolecular octahedra with a +12 charge and anionic inorganic clusters with a -10 charge. However, 1M1 contains M1 ions in place of the H3O+ ions in 1Na, and furthermore, a novel rhombic dodecahedron cluster composed of 14 nitrate ions, which encapsulates two M2 ions, is formed in each hydrophilic tetrahedral interstice in 1M2.

Unusual Hexanuclear Fe(II, III) Pyrazole–Pyrazolate–Pivalate Formed upon η5,π-Bonding of Bridging Pyrazolate Anion to Potassium Cation

The reaction of aqueous iron(II) sulfate with potassium pivalate in MeCN followed by removal of the solvent and dissolution of the residue in Et3N and hexane gives a brown solution and a white precipitate. The reaction of the mother liquor with excess 3,5-dimethylpyrazole (HDmpz) afforded the hexanuclear complex {[Fe3(µ3-O)(µ-OOCtBu)4(OOCtBu)2(HDmpz)(µ,η5-Dmpz)(µ-K)]2 ∙ 2HDmpz} (I). The complex was characterized by elemental analysis, IR spectroscopy, and X-ray diffraction (CIF file CCDC no. 1956015). Complex I is formed upon deprotonation of HDmpz, which was observed for the first time in the presence of iron carboxylates. Deprotonation gives the bridging pyrazolate anion, which assembles two trinuclear Fe3(µ3-O)(µ-OOCtBu)4(OOCtBu)2(HDmpz) moieties into a hexanuclear cluster though unusual η5,π-coordination with the potassium cation.

Bismuth and Titanium Phosphinates: Isolation of Tetra-, Hexa- and Octanuclear Clusters.

The reaction of organobismuth precursors with trityl-H-phosphinic acid in varying reaction conditions afforded colorless crystals, whose single crystal X-ray characterization revealed the formation of monomer {(Ph3Bi)[(Ph3C)(H)PO2]2}·3/2(CH3CN)2.1/2H2O (1) and butterfly shaped tetranuclear cluster Bi4(μ3-O)2[(Ph3C)(H)(PO2)]8·2CH2Cl2·1/2CH3CN.2H2O (2). The reaction of titanium isopropoxide with two different phosphinic acids trityl-H-phosphinic acid and cycP(O)(OH) led to isolation of cubane type octahedral complex {Ti8(μ2-O)8(μ2-OH)4[(Ph3C)(H)PO2]12}[3C7H8] (3) and hexanuclear complex Ti6(μ2-cycPO2)9(μ2-O)6(μ2-OH)3·4CH3CN·4H2O (4) respectively.

Hetero-hexalanthanide Complexes: A New Synthetic Strategy for Molecular Thermometric Probes.

Reactions in solvothermal or microwave-assisted conditions between a hexanuclear rare-earth entity ([Ln6] with Ln = Eu-Dy) and m-halogeno-benzoic acids lead to three series of isostructural complexes with respective chemical formulas [Ln6(μ3-OH)2(H2O)2(NO3)2(3-cb)14]·4CH3CN, [Ln6(μ3-OH)2(H2O)2(NO3)2(3-bb)14]·6CH3CN, and [Ln6(μ3-OH)2(H2O)2(NO3)2(3-ib)14]·6CH3CN, where 3-cb-, 3-bb-, and 3-ib- represent 3-chloro-, 3-bromo-, and 3-iodo-benzoate, respectively. These three series of compounds are almost isostructural. Their luminescent properties, in the solid and solution states, have been studied in detail and compared. This study shows that hexanuclear complexes own strong intermetallic energy transfers. This makes these complexes good candidates for thermometric probes in solid state or in solution state.

Effect of local ordering around Th4+ ions in glycine-nitrate precursor gel on the powder characteristic of gel-combusted ThO2

In the present study, influence of local environment around Th4+ ions in the precursor gel on the powder characteristics of combusted product (ThO2) is investigated in detail. Partial crystallization of Th4+ complexes having different number of glycine and NO3− species in glycine-thorium nitrate aqueous gel has been confirmed by DSC and SAXS studies. Further, combining SAXS and FT-IR results with existing speciation studies, it is inferred that, varying concentrations of mono- and hexanuclear Th4+-glycine-NO3- complexes are formed in the precursor gel depending upon the fuel to oxidant ratio (F:O). Lower F:O values lead to predominance of hexanuclear Th4+-glycine-NO3- complexes with excess NO3− ions in its vicinity while higher F:O value (F:O = 1.25) results in predominant formation of monocular Th4+-glycine-NO3- complexes. Combustion of gel consisting of mononuclear complexes leads to smaller ThO2 crystallites as compared to hexanuclear complexes as the Th4+--Th4+ distances are larger in the former compared to the latter. The above mentioned complex species are responsible for the observed bimodal crystallite size distribution in nanocrystalline ThO2 powder prepared upon combustion of gel precursor.

Synthesis of an Emissive Spectacle-Shaped Hexanuclear Rhenium(I) Complex.

Ring-shaped multinuclear Re(I) complexes (Re(I) rings) have the potential to function as useful units in multifarious photofunctional compounds because of their flexibility in molecular design and various photofunctions. The first synthetic example of the coupling reaction using a Re(I) ring as a building block to synthesize a novel spectacle-shaped hexanuclear complex is reported herein. This complex shows an efficient intramolecular energy transfer to accumulate the excitation energy into the central Re(I) units, and has suitable photophysical properties as a photosensitizer.