Solvent-Induced Formation of Novel Ni(II) Complexes Derived from Bis-Thiosemicarbazone Ligand: An Insight from Experimental and Theoretical Investigations

In this work, we report solvent-induced complexation properties of a new N2S2 tetradentate bis-thiosemicarbazone ligand (H2LI), prepared by the condensation of 4-phenylthiosemicarbazide with bis-aldehyde, namely 2,2’-(ethane-1,2-diylbis(oxy)dibenzaldehyde, towards nickel(II). Using ethanol as a reaction medium allowed the isolation of a discrete mononuclear homoleptic complex [NiLI] (1), for which its crystal structure contains three independent molecules, namely 1-I, 1-II, and 1-III, in the asymmetric unit. The doubly deprotonated ligand LI in the structure of 1 is coordinated in a cis-manner through the azomethine nitrogen atoms and the thiocarbonyl sulfur atoms. The coordination geometry around metal centers in all the three crystallographically independent molecules of 1 is best described as the seesaw structure. Interestingly, using methanol as a reaction medium in the same synthesis allowed for the isolation of a discrete mononuclear homoleptic complex [Ni(LII)2] (2), where LII is a monodeprotonated ligand 2-(2-(2-(2-(dimethoxymethyl)phenoxy)ethoxy)benzylidene)-N-phenylhydrazine-1-carbothioamide (HLII). The ligand LII was formed in situ from the reaction of LI with methanol upon coordination to the metal center under synthetic conditions. In the structure of 2, two ligands LII are coordinated in a trans-manner through the azomethine nitrogen atom and the thiocarbonyl sulfur atom, also yielding a seesaw coordination geometry around the metal center. The charge and energy decomposition scheme ETS-NOCV allows for the conclusion that both structures are stabilized by a bunch of London dispersion-driven intermolecular interactions, including predominantly N–H∙∙∙S and N–H∙∙∙O hydrogen bonds in 1 and 2, respectively; they are further augmented by less typical C–H∙∙∙X (where X = S, N, O, π), CH∙∙∙HC, π∙∙∙π stacking and the most striking, attractive long-range intermolecular C–H∙∙∙Ni preagostic interactions. The latter are found to be determined by both stabilizing Coulomb forces and an exchange-correlation contribution as revealed by the IQA energy decomposition scheme. Interestingly, the analogous long-range C–H∙∙∙S interactions are characterized by a repulsive Coulomb contribution and the prevailing attractive exchange-correlation constituent. The electron density of the delocalized bonds (EDDB) method shows that the nickel(II) atom shares only ~0.8|e| due to the σ-conjugation with the adjacent in-plane atoms, demonstrating a very weak σ-metalloaromatic character.

A remarkable fluorescent cerium-based chemosensor for selective phosphate detection in aquaeous medium

<p>Phosphates anions are important molecules for the society in general and involved for example in medicine or agriculture. Detection of them with chemosensor is a challenge due to the chemical properties of the anions. In this context, an exquisite chemosensor would have exquisite affinity, selectivity and low detection limit. Here we address this problem using a simple fluorescent indicator displacement assay (FID) with only commercially available chemicals used to probe phosphate ions in aqueous medium using cerium ammonium nitrate (CAN). The monomeric homoleptic complex detects phosphate ions in low millimolar concentrations either spectrophotometrically or with the naked-eye with high selectivity over other anions and high affinity. To our knowledge, this is the first description of a simple sensitive, selective and high affinity cerium-based chemosensor for the fluorescent selective naked-eye detection of phosphate in aqueous medium. It proved useful for the detection of phosphate in Coca Cola. </p>

A biomimetic cerium-based biosensor for the direct visual detection of phosphate under physiological conditions

<div><div><div><p> </p><p>An indicator displacement assay (IDA) was used to probe phosphate ions in acqueous medium at neutral pH using a dinuclear cerium based complex [Ce₂(HXTA)]3+. The homoleptic complex can be used to detect phosphate ions in micromolar concentrations either spectrophotometrically or with the naked-eye. To our knowledge, this is the biomimetic detection system with the highest affinity known to date for selective, naked-eye based phosphate recognition under physiological conditions.</p> </div></div></div>

A biomimetic cerium-based biosensor for the direct visual detection of phosphate under physiological conditions

<div><div><div><p> </p><p>An indicator displacement assay (IDA) was used to probe phosphate ions in acqueous medium at neutral pH using a dinuclear cerium based complex [Ce₂(HXTA)]3+. The homoleptic complex can be used to detect phosphate ions in micromolar concentrations either spectrophotometrically or with the naked-eye. To our knowledge, this is the biomimetic detection system with the highest affinity known to date for selective, naked-eye based phosphate recognition under physiological conditions.</p> </div></div></div>

A New Family of Homoleptic Copper Complexes of Curcuminoids: Synthesis, Characterization and Biological Properties

We report herein the synthesis and crystal structures of five new homoleptic copper complexes of curcuminoids. The scarcity of reports of homoleptic complex structures of curcuminoids is attributed to the lack of crystallinity of such derivatives, and therefore, their characterization by single crystal X-ray diffraction is rare. The ligand design suppressing the phenolic interaction by esterification or etherification has afforded a significant increase in the number of known crystal structures of homoleptic metal complexes of curcuminoids revealing more favorable crystallinity. The crystal structures of the present new copper complexes show four-fold coordination with a square planar geometry. Two polymorphs were found for DiBncOC-Cu when crystallized from DMF. The characterization of these new complexes was carried out using infrared radiation (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and single crystal X-ray diffraction (SCXRD) and the antioxidant and cytotoxic activity of the obtained complexes was evaluated.

A naked-eye [Ce2(HXTA)]3+ based biosensor for the detection of phosphate ions in Water

<div><div><div><p>An indicator displacement assay (IDA) was used to probe phosphate ions in water using a dinuclear cerium based complex [Ce₂(HXTA)]³⁺. The homoleptic complex is able to detect phosphates ions in micromolar concentrations both spectrophotometrically and with the naked-eye</p></div></div></div>

Controlling the lability of uranyl(vi) through intramolecular π–π stacking

A reaction of UO22+ with cyclohexyldiphenylphosphine oxide (OPCyPh2) in ethanol resulted in a perchlorate salt of the 4-fold homoleptic complex, [UO2(OPCyPh2)4](ClO4)2·EtOH.

Solvent dependence of the solid-state structures of salicylaldiminate magnesium amide complexes

There are challenges in using magnesium coordination complexes as reagents owing to their tendency to adopt varying aggregation states in solution and thus impacting the reactivity of the complexes. Many magnesium complexes are prone to ligand redistributionviaSchlenk equilibrium due to the ionic character within the metal–ligand interactions. The role of the supporting ligand is often crucial for providing stability to the heteroleptic complex. Strategies to minimize ligand redistribution in alkaline earth metal complexes could include using a supporting ligand with tunable sterics and electronics to influence the degree of association to the metal atom. Magnesium bis(hexamethyldisilazide) was reacted with salicylaldimines [1L=N-(2,6-diisopropylphenyl)salicylaldimine and2L= 3,5-di-tert-butyl-N-(2,6-diisopropylphenyl)salicylaldimine] in either nondonor (toluene) or donor solvents [tetrahydrofuran (THF) or pyridine]. The structures of the magnesium complexes were studied in the solid stateviaX-ray diffraction. In the nondonor solvent,i.e.toluene, the heteroleptic complex bis{μ-2-[(2,6-diisopropylphenyl)iminomethyl]phenolato}-κ3N,O:O;κ3O:N,O-bis[(hexamethyldisilazido-κN)magnesium(II)], [Mg2(C19H22NO)2(C6H18NSi2)2] or [1LMgN(SiMe3)2]2, (1), was favored, while in the donor solvent,i.e.pyridine (pyr), the formation of the homoleptic complex {2,4-di-tert-butyl-6-[(2,6-diisopropylphenyl)iminomethyl]phenolato-κ2N,O}bis(pyridine-κN)magnesium(II) toluene monosolvate, [Mg(C27H38NO)2(C5H5N)2]·C5H5N or [{2L2Mg2(pyr)2}·pyr], (2), predominated. Heteroleptic complex (1) was crystallized from toluene, while homoleptic complexes (2) and the previously reported [1L2Mg·THF] [Quinqueet al.(2011).Eur. J. Inorg. Chem.pp. 3321–3326] were crystallized from pyridine and THF, respectively. These studies support solvent-dependent ligand redistribution in solution.In-situ1H NMR experiments were carried out to further probe the solution behavior of these systems.