Role of Redox-Inactive Metal Ions in Modulating the Reduction Potential of Uranyl Schiff Base Complexes: Detailed Experimental and Theoretical Studies.

A mononuclear uranyl complex, [UOL] (), has been synthesized with the ligand ,'-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane (HL). The complex showed a reversible U(VI)/U(V) redox couple in cyclic voltammetric measurements. The reduction potential of this couple showed a positive shift upon the addition of redox-inactive alkali- and alkaline-earth Lewis acidic metal ions (Li, Na, K, Ca, Sr, and Ba) to an acetonitrile solution of complex .

Reaction of Cu(II) Chelates with Uranyl Nitrate to Form a Coordination Complex or H-Bonded Adduct: Experimental Observations and Rationalization by Theoretical Calculations.

Four new heterometallic Cu(II)-U(VI) species, [{(CuL)(CHCN)}UO(NO)] (), [{CuL)(CHCN)}UO(NO)] (), [{(CuL)(HO)}UO(NO)] (), and [UO(NO)(HO)]·2[CuL]·HO (), were synthesized using four different metalloligands ([CuL], [CuL], [CuL], and [CuL], respectively) derived from four unsymmetrically dicondensed N,O-donor Schiff bases. Single-crystal structural analyses revealed that complexes , , and have a discrete dinuclear [Cu-UO] core in which one metalloligand, [CuL], is connected to the uranyl moiety via a double phenoxido bridge. Two chelating nitrate ions complete the octa-coordination around uranium.

Elucidating the secondary effect in the Lewis acid mediated anodic shift of electrochemical oxidation of a Cu(ii) complex with a NO donor unsymmetrical ligand.

A metalloligand [CuL] (H2L = N-α-methylsalicylidene-N'-salicylidene-1,3-propanediamine) was reacted with a series (Li+, Na+, K+, Mg2+, Ca2+, Zn2+, Cd2+, Pr3+, Nd3+ and Sm3+) of redox-inactive metal ions (in excess) with different Lewis acidities in acetonitrile to form heterometallic complexes in situ. In the cases of K+ and Zn2+, single crystals were isolated from their respective solutions and solved. The complexes were found to be trinuclear with the phenoxido bridge between the redox-inactive metals and the copper center having closest equilibrium distance.

Structural variations in (CuL)Ln complexes of a series of lanthanide ions with a salen-type unsymmetrical Schiff base(HL): Dy and Tb derivatives as potential single-molecule magnets.

A new series of heterometallic trinuclear CuLn complexes [lanthanide ions Ln = Gd (1), Tb (2), Dy (3), Ho (4) and Er (5)] has been synthesized using a Cu(ii)-metalloligand derived from a NO donor unsymmetrical Schiff base, HL (where HL = N-α-methylsalicylidene-N'-salicylidene-1,3-propanediamine), and structurally characterized. Among these complexes, [(CuL)Gd(NO)(CHCN)] (1), [(CuL)Tb(NO)(CHCN)] (2) and [(CuL)Dy(NO)(CHCN)] (3) are isomorphic and isostructural. In these complexes two metalloligands coordinate to the central Ln(iii) (Ln = Gd, Tb and Dy respectively) ion in a transoid fashion viaμ-phenoxido oxygen atoms.

Subtle Structural Changes in (CuL)Mn Complexes To Induce Heterometallic Cooperative Catalytic Oxidase Activities on Phenolic Substrates (HL = Salen Type Unsymmetrical Schiff Base).

A new Cu(II) complex of an asymmetrically dicondensed Schiff base (HL = N-(2-hydroxyacetophenylidene)-N'-salicylidene-1,3-propanediamine) derived from 1,3-propanediamine, salicylaldehyde, and o-hydroxyacetophenone has been synthesized. Using this complex, [CuL] (1), as a metalloligand, two new trinuclear Cu-Mn complexes, [(CuL)Mn(N)(HO)](ClO)·HO (2) and [(CuL)Mn(NCS)] (3), have been prepared. Single-crystal structural analyses reveal that complexes 2 and 3 both have the same bent trinuclear {(CuL)Mn} structural unit in which two terminal bidentate square-planar (CuL) units are chelated to the central octahedral Mn(II) ion.

Strong ferromagnetic exchange interactions in hinge-like Dy(O2Cu)2 complexes involving double oxygen bridges.

Two trinuclear isomeric compounds, [{(Cu(II)(salpn))(Me(CO)Me)}2Dy(III)(NO3)3] (1) and [{Cu(II)(salpn)}2Dy(III)(H2O)(NO3)3]·MeOH (2), along with one polymeric compound, {[{Cu(II)(salpn)}2Dy(III)(NO3)3bpy]·MeOH·H2O}n (3), were synthesized using a metalloligand, [Cu(II)(salpn)], where H2salpn and bpy stand for N,N'-bis(salicylidene)-1,3-propanediamine and 4,4'-bipyridine, respectively. Compounds 1 and 2 were selectively prepared with two solvents: the less polar acetone led to the exclusive crystallization of 1 with a transoid trinuclear architecture, while more polar solvent methanol provided sole construction of 2 with a cisoid trinuclear architecture. Compound 3 was prepared from 1 or 2 after bpy was introduced as a bridge.

Trinuclear heterometallic Cu(II)-Mn(II) complexes of a salen type Schiff base ligand: anion dependent variation of phenoxido bridging angles and magnetic coupling.

Five new trinuclear heterometallic Cu(II)-Mn(II) complexes [(CuL)2Mn(O2CPh)2] (1), [(CuL)2Mn(N3)2] (2), [(CuL)2Mn(NCO)2] (3), [(CuL)2Mn(NO3)2] (4) and [(CuL)2Mn(Sal)2]·CH2Cl2 (5) have been synthesized with the di-Schiff base ligand H2L (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine and Sal = salicylate). These complexes with different anionic co-ligands have been synthesized to attain a large variation in phenoxido bridging angles and to investigate its consequence on magnetic properties. Single crystal X-ray diffraction analyses reveal that complexes 1, 2, 4 and 5 are linear, whereas 3 has an angular geometry.

Solvent-templated supramolecular isomerism in 2D coordination polymer constructed by Ni(II)2Co(II) nodes and dicyanamido spacers: drastic change in magnetic behaviours.

Two heterometallic coordination polymers (CPs) have been prepared using [Ni(II)L]2Co(II) (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) as nodes and dicyanamido spacers by varying the solvent for synthesis. Structural characterizations revealed that methanol assisted the formation of a two-dimensional (4,4) connected rhombic grid network of [(NiL)2Co(NCNCN)2]∞ (1a) whereas relatively less polar acetonitrile afforded a different superstructure {[(NiL)2Co(NCNCN)2]·CH3CN}∞ (1b) with a two-dimensional (4,4) connected square grid network. The presence of acetonitrile molecules in the structure of 1b seems to change the spatial orientation of the terminal metalloligands [NiL] from pseudo-eclipsed in 1a to staggered-like in 1b around the central Co(II).

Use of metalloligands [CuL] (H2L = salen type di-Schiff bases) in the formation of heterobimetallic copper(II)-uranyl complexes: photophysical investigations, structural variations, and theoretical calculations.

Five heterobimetallic copper(II)-uranium(VI) complexes [(CuL(1))UO2(NO3)2] (1), [{CuL(1)(CH3CN)}UO2(NO3)2] (2), [{CuL(1)(CH3COCH3)}UO2(NO3)2] (3), [{CuL(2)(CH3CN)}UO2(NO3)2](4), and [{CuL(2)(CH3COCH3)}UO2(NO3)2][{CuL(2)}UO2(NO3)2] (5) have been synthesized by reacting the Cu(II)-derived metalloligands [CuL(1)] and [CuL(2)] (where, H2L(1) = N,N'-bis(α-methylsalicylidene)-1,3-propanediamine and H2L(2) = N,N'-bis(salicylidene)-1,3-propanediamine) with UO2(NO3)2·6H2O in 1:1 ratio by varying the reaction temperature and solvents. Absorption and fluorescence quenching experiments (steady-state and time-resolved) indicate the formation of 1:1 ground-state charge transfer copper(II)-uranium(VI) complexes in solution. X-ray single-crystal structure reveals that each complex contains diphenoxido bridged Cu(II)-U(VI) dinuclear core with two chelated nitrato coligands.