Rare Nuclearities in Ni(II) Cluster Chemistry: An Unprecedented {Ni12} Nanosized Cage from the Use of N-Naphthalidene-2-Amino-5-Chlorobenzoic Acid

The self-assembly reaction between NiI2, benzoic acid (PhCO2H) and the Schiff base chelate, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in the presence of the organic base triethylamine (NEt3), has resulted in the isolation and the structural, spectroscopic, and physicochemical characterization of the dodecanuclear [Ni12I2(OH)6(O2CPh)5(nacb)5(H2O)4(MeCN)4]I (1) cluster compound in ~30% yield. Complex 1 has a cage-like conformation, comprising twelve distorted, octahedral NiII ions that are bridged by five μ3-OH−, one μ-OH−, an I− in 55% occupancy, five PhCO2− groups (under the η1:η1:μ, η1:η2:μ3 and η2:η2:μ4 modes), and the naphthoxido and carboxylato O-atoms of five doubly deprotonated nacb2− groups. The overall {Ni12} cluster exhibits a nanosized structure with a diameter of ~2.5 nm and its metallic core can be conveniently described as a series of nine edge- or vertex-sharing {Ni3} triangular subunits. Complex 1 is the highest nuclearity coordination compound bearing the nacbH2 chelate, and a rare example of polynuclear NiII complex containing coordinating I− ions. Direct current (DC) magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the NiII ions, while photophysical studies of 1 in the solid-state showed a cyan-to-green centered emission at 520 nm, upon maximum excitation at 380 nm. The reported results demonstrate the rich coordination chemistry of the deprotonated nacb2− chelate in the presence of NiII metal ions, and the ability of this ligand to adopt a variety of different bridging modes, thus fostering the formation of high-nuclearity molecules with rare, nanosized dimensions and interesting physical (i.e., magnetic and optical) properties.

A new binuclear NiII complex with tetrafluorophthalate and 2,2′-bipyridine ligands: synthesis, crystal structure and magnetic properties

A new NiII compound, [Ni2(tfpa)2(bipy)2(H2O)4] (1) with tetrafluorophthalate (tfpa2−) and 2,2′-bipyridine (abbreviated as bipy) ligands, has been synthesized and structurally characterized. The single-crystal X-ray diffraction analysis reveals that the tfpa2− anions act as bis-monodentate linkers connecting NiII centers to form the dinuclear structure of 1. The dimeric units are stabilized by intramolecular π–π stacking and are further connected into a layer through O–HLO hydrogen bonding. Variable-temperature magnetic susceptibility data in the 10–200 K temperature range indicate weak ferromagnetic coupling between the two NiII ions.

A Ternary Nickel(II) Schiff Base Complex Containing Di-anionic and Neutral Forms of a Dithiocarbazate Schiff Base

The title NiII complex, Ni(L)(LH2) (1), where LH2 is S-2-methybenzyl-β-N-(2-hydroxy-3-methoxybenzylmethylene) dithiocarbazate, was isolated from the reaction of Ni(acetate)2·4H2O and two molar equivalents of LH2. The complex was characterized by elemental analysis, spectroscopy (IR and UV) as well as by a single-crystal X-ray structure determination. The nickel(II) center is coordinated within a cis-NOS2 donor set that defines a square planar geometry. Three donor atoms, i.e., N, O, and S, are provided by a doubly deprotonated S-2-methybenzyl-β-N-(2-hydroxy-3-methoxybenzylmethylene) dithiocarbazate ligand while the fourth donor, i.e., a thione-S, comes from the neutral form of the dithiocarbazate ligand. In the LH2 ligand, an intramolecular hydroxy-O-H…N(imine) hydrogen bond is found. There is also an intra-ligand, charge assisted amine-N-H…O(phenoxide) hydrogen bond. A notable feature of the molecular packing is the formation of supramolecular chains sustained by π…π stacking interactions whereby the interacting rings are the five- and six-membered chelate and methoxybenzene rings. The chains are connected into a three-dimensional architecture by methyl-C-H…O(methoxy), methoxy-C-H…S(ester), and tolyl-C-H…π(tolyl) interactions.

A NiII complex of the tetradentate salen ligand H2LNH2 comprising an anchoring –NH2 group: synthesis, characterization and electrocatalytic CO2 reduction to alcohols

A new salen ligand with an anchoring free amine functional group in the ligand backbone and the corresponding NiII complex [NiIILNH2] (1) were synthesized and characterized. Complex 1 electrocatalytically reduced CO2 to alcohols.

A strongly fluorescent NiII complex with 2-(2-hydroxyethyl)pyridine ligands: synthesis, characterization and theoretical analysis and comparison with a related polymeric CuII complex

The synthesis and characterization of diaquabis[2-(2-hydroxyethyl)pyridine-κ2 N,O)nickel(II) dinitrate, [Ni(C7H9NO)2(H2O)2](NO3)2, under ambient conditions is reported and compared with catena-poly[[bis[2-(2-hydroxyethyl)pyridine-κ2 N,O]copper(II)]-μ-sulfato-κ2 O:O′], [Cu(C7H9NO)2(SO4)] n [Zeghouan et al. (2016). Private communication (refcode 1481676). CCDC, Cambridge, England]. In the two complexes, the 2-(2-hydroxyethyl)pyridine ligands coordinate the metal ions through the N atom of the pyridine ring and the O atom of the hydroxy group, creating a chelate ring. The NiII or CuII ion lies on an inversion centre and exhibits a slightly distorted MO4N2 octahedral coordination geometry, build up by O and N atoms from two 2-(2-hydroxyethyl)pyridine ligands and two water molecules or two O atoms belonging to sulfate anions. The sulfate anion bridges the CuII ions, forming a polymeric chain. The photoluminescence properties of these complexes have been studied on as-synthesized samples and reveal that both compounds display a strong blue-light emission with maxima around 497 nm. From DFT/TDDFT studies, the blue emission appears to be derived from the ligand-to-metal charge-transfer (LMCT) excited state. In addition, the IR spectroscopic properties and thermogravimetric behaviours of both complexes have been investigated.

Indirect evidence for a NiIII–oxyl oxidant in the reaction of a NiII complex with peracid

The oxidation of a NiII complex with m-CPBA is shown to promote the formation of a transient NiIII–O˙ species. Methine C–H bond activation in the supporting ligand by this species led to a benzoxazine product.

Redox and photocatalytic properties of a NiII complex with a macrocyclic biquinazoline (Mabiq) ligand

Upon irradiation with visible light, the NiII complex 1 is converted to the reduced form 2 in the presence of NEt3. The Ni-based photosensitizer catalyzes the cyclization of a bromoalkyl-substituted indole.