Organo-Functionalized Lacunary Double Cubane-Type Oxometallates: Synthesis, Structure, and Properties of [(MII Cl)2 (VIV O)2 {((HOCH2 CH2 )(H)N(CH2 CH2 O))(HN(CH2 CH2 O)2 )}2 ] (M=Co, Zn).

Organofunctionalized tetranuclear clusters [(MII Cl)2 (VIV O)2 {((HOCH2 CH2 )(H)N(CH2 CH2 O))(HN(CH2 CH2 O)2 )}2 ] (1, M=Co, 2: M=Zn) containing an unprecedented oxometallacyclic {M2 V2 Cl2 N4 O8 } (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo-alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single-crystal X-ray diffraction structure analysis. The isostructural clusters are formed of edge-sharing octahedral {VO5 N} and trigonal bipyramidal {MO3 NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of 1 and 2 in an unusual two-mode fashion, unobserved previously. In the crystalline state, the clusters of 1 and 2 are joined by hydrogen bonds to form a three-dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [Jiso (VIV -VIV )=-5.4(1); -3.9(2) cm-1 ], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [Jiso (VIV -CoII )=-12.6 and -7.5 cm-1 ] contained in 1.

Alloyed Tetranuclear Metal Chains of Pd4-n Ptn (n=0-3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge.

A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd4-n Ptn (µ-rac-dpmppan)2 (XylNC)2 ](PF6 )2 (XylNC=xylyl isocyanide; n=0: Pd4 (1), 1: PtPd3 (2), 2: PtPd2 Pt (3), 2: Pt2 Pd2 (4), 3: Pt2 PdPt (5)), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31 P{1 H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1-5 exhibited characteristic bands at 635-510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd4 chain.

Strongly luminous tetranuclear gold(I) complexes supported by tetraphosphine ligands, meso- or rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane.

A series of tetragold(I) complexes supported by tetraphosphine ligands, meso- and rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (meso- and rac-dpmppm) were synthesized and characterized to show that the tetranuclear Au(I) alignment varies depending on syn- and anti-arrangements of the two dpmppm ligands with respect to the metal chain. The structures of syn-[Au4 (meso-dpmppm)2X]X'3 (X = Cl; X' = Cl (4 a), PF6 (4 b), BF4 (4 c)) and syn-[Au4 (meso-dpmppm)2]X4 (X = PF6 (4 d), BF4 (4 e), TfO (4 f); TfO = triflate) involved a bent tetragold(I) core with a counter anion X incorporated into the bent pocket. Complexes anti-[Au4 (meso-dpmppm)2]X4 (X = PF6 (5 d), BF4 (5 e), TfO (5 f)) contain a linearly ordered Au4 string and complexes syn-[Au4 (rac-dpmppm)2X2]X'2 (X = Cl, X' = Cl (6 a), PF6 (6 b), BF4 (6 c)) and syn-[Au4 (rac-dpmppm)2]X4 (X = PF6 (6 d), BF4 (6 e), TfO (6 f)) consist of a zigzag tetragold(I) chain supported by the two syn-arranged rac-dpmppm ligands. Complexes 4 d-f, 5 d-f, and 6 d-f with non-coordinative large anions are strongly luminescent in the solid state (λmax = 475-515 nm, Φ = 0.67-0.85) and in acetonitrile (λmax = 491-520 nm, Φ = 0.33-0.97); the emission was assigned to phosphorescence from (3) [dσ*σ*σ* pσσσ] excited state of the Au4 centers on the basis of DFT calculations as well as the long lifetime (a few µs). The emission energy is predominantly determined by the HOMO and LUMO characters of the Au4 centers, which depend on the bent (4), linear (5), and zigzag (6) alignments. The strong emissions in acetonitrile were quenched by chloride anions through simultaneous dynamic and static quenching processes, in which static binding of chloride ions to the Au4 excited species should be the most effective. The present study demonstrates that the structures of linear tetranuclear gold(I) chains can be modified by utilizing the stereoisomeric tetraphosphines, meso- and rac-dpmppm, which may lead to fine tuning of the strongly luminescent properties intrinsic to the Au(I) 4 cluster centers.

A Tetranuclear Copper(II)/Calcium(II) Complex as Dual Chemosensor for Colorimetric and Fluorescent Detection of Non-Steroidal Anti-Inflammatory Drugs.

The tetranuclear Cu2+ /Ca2+ /Ca2+ /Cu2+ complex based on Malten ligand has been investigated as a platform for anion binding. Simple organic carboxylates and non-steroidal anti-inflammatory drugs (NSAIDs) have been tested, revealing the ability of the platform to bind them. The receiving platform hosts at least two guests in solution although a third anion can be bound, as suggested by X-ray diffraction analysis. The addition of the anions is accompanied by a color change of the solution, making the system a colorimetric sensor for carboxylates (LOD values comprised between 3.6 and 20.7 ppm). A fluorescent system consisting of the 2-(3-oxido-6-oxoxanthen-9-yl)benzoate (fluorescein anion) linked to the tetranuclear platform has been also prepared and used in a chemosensing ensemble approach to signal the presence of the selected anions (Log K between 2.6 and 5.6 for the addition of two guests). The latter also works in a paper strip test, offering the chemosensor a possible practical application.

Effect of structural variation on enzymatic activity in tetranuclear (Cu4) clusters with defective cubane core.

The stimulus to the modeling of enzyme functioning sites comes from their potential to give insight into the natural enzyme's mechanistic pathways, ascertain the role of that different metal ion in the active site and construct better catalysts motivated by nature. The presence of metal ion leads to the activation of molecular oxygen in the metalloenzymes. The metalloenzymes such as the catechol oxidase (CO) enzyme that oxidizes the catechol to corresponding quinones which eventually protect damage tissues from plant and pathogen. Thus, the design and characterization of catalysts used as selectively and efficiently oxidation reactions have grown to be unique challenges for modern inorganic chemists. In this work, two novel tetranuclear complexes (1 and 2) have been synthesized in excellent yield. The complexes were characterized using various spectroscopic techniques such as FTIR, UV-Visible and PXRD pattern. The structure of 1 and 2 was elucidated by SC-XRD (single crystal X-ray diffraction) analysis. The magnetic study reveals the presence of the antiferromagnetic nature of 1 and 2. Both 1 and 2 shows a very good catecholase-like activity by oxidizing the catechol to analogous quinone in methanolic solution. Thus, a structure-activity relationship can further help us design other substituted tetranuclear complexes with enhanced catecholase like activity.Communicated by Ramaswamy H. Sarma.

Hetero-Tetranuclear Cu2+ /Ca2+ /Ca2+ /Cu2+ Architectures Based On Malten Ligand: Scaffold for Anion Binding.

The hetero-tetranuclear Cu2+ /Ca2+ /Ca2+ /Cu2+ complex obtained with the N,N'-bis((3-hydroxy-4-pyron-2-yl)methyl)-N,N'-dimethylethylendiamine (Malten) ligand has been studied in solid and solution states as scaffold to bind anions. Three crystal structures showing the same metal ions sequence have been examined; they display a tetracharged complex cation neutralized by four monocharged anions. The anions play two different roles: as coordinated (two ClO4- , Cl- or NO3- ) or ancillary (two ClO4- ) guests. The tetranuclear scaffold hosts two anions also in aqueous and ethanol solutions. Spectrophotometric studies in ethanol allowed to determine the addition constant values for Cl- and Br- (Log K1-2 =4.43(4), 4.39(3) for Cl- , 3.80(3), 3.54(2) for Br- ) while the others, although bound, showed lower affinity for the scaffold. Both the crystals and the solutions change their color depending on the added anion, namely pink, dark green or blue in the presence of ClO4- , Cl- or NO3- , respectively, thus the presence of the different anions is visible to the naked eye. The hetero-tetranuclear Cu2+ /Ca2+ /Ca2+ /Cu2+ complex is a versatile architecture to be used as scaffold for anion binding.

A Fully Characterized Complex Ion with Unreduced TCNQ as Fourfold Bridging Ligand: [(µ4 -TCNQ){fac-Re(CO)3 (bpy)}4 ]4+ .

Innocent behavior of a typical non-innocent ligand has been observed for the first structurally characterized discrete metal complex with tetranucleating TCNQ. The coordination of four [Re(CO)3 (bpy)]+ units (see picture: C: black, N: green, O: blue, Re: red) facilitates the reduction of the already excellent π-acceptor molecule TCNQ by a further 0.74 V! TCNQ=7,7,8,8-tetracyano-p-quinodimethane, bpy=2,2'-bipyridine.