Nickel Thiocyanate Research Articles

Multifunctional (4-in-1) Therapeutic Applications of Nickel Thiocyanate Nanoparticles Impregnated Cotton Gauze as Antibacterial, Antibiofilm, Antioxidant and Wound Healing Agent.

The wounds, arises from accidents, burns, surgeries, diabetes, and trauma, can significantly impact well-being and present persistent clinical challenges. Ideal wound dressings should be flexible, stable, antibacterial, antioxidant and anti-inflammatory in nature, facilitating a scarless rapid wound healing. Initiatives were taken to create antibacterial cotton fabrics by incorporating agents like antibiotics and metallic nanoparticles. However, due to a lack of multifunctionality, these materials were not highly effective in causing scarless and rapid wound healing. In this article, nickel thiocyanate nanoparticle (NiSCN-NPs) impregnated cotton gauze wound dressing (NiSCN-CG) was developed. These nanoparticles were non-toxic to normal human cell lines till 1 mg/mL dose and did not cause skin irritation in the rat model. Further, NiSCN-NPs exhibited antimicrobial, antibiofilm and antioxidant activities confirmed using different in vitro experiments. In vivo wound healing studies in rat models using NiSCN-CG demonstrated rapid scarless wound healing. The nickel thiocyanate impregnated cotton gauze presents a novel approach in scarless wound healing, and as an antimicrobial agent, offering a promising solution for diverse wounds and infections in the future.

Nickel(II) Thiocyanate Complex as a Catalyst for Cross-Coupling Reactions

AbstractA nickel thiocyanate complex was prepared by the reaction of Ni(NCS)2 with (2S,3S)-2,3-bis(diphenylphosphino)butane (Chiraphos) by following a method reported in the literature. The resulting nickel complex was found to be active in the polymerization reactions of 1,4-dihalobenzenes and 2-halo-3-hexylthiophenes, leading to poly-1,4-phenylenes and poly(3-hexylthiophene-2,5-diyl), respectively. The polymerization in the presence of similar catalysts containing other ligands, such as 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or N-heterocyclic carbenes, also proceeded in a similar manner. Ni(NCS)2 complexes also successfully catalyzed Suzuki–Miyaura couplings and Buchwald–Hartwig aminations to afford the corresponding biaryls and arylamines, respectively.

Syntheses and crystal structures of the ethanol, acetonitrile and diethyl ether Werner clathrates bis-(iso-thio-cyanato-κN)tetra-kis-(3-methyl-pyridine-κN)nickel(II).

The reaction of nickel(II)thio-cyanate with 3-methyl-pyridine (3-picoline; C6H7N) in different solvents leads to the formation of crystals of bis-(iso-thio-cyanato-κN)tetra-kis-(3-methyl-pyridine-κN)nickel(II) as the ethanol disolvate, [Ni(NCS)2(C6H7N)4]·2C2H5OH (1), the acetonitrile disolvate, [Ni(NCS)2(C6H7N)4]·2CH3CN (2), and the diethyl ether monosolvate, [Ni(NCS)2(C6H7N)4]·C4H10O (3). The crystal structures of these compounds consist of NiII cations coordinated by two N-bonded thio-cyanate anions and four 3-methyl-pyridine ligands to generate NiN6 octa-hedra with the thio-cyanate groups in a trans orientation. In compounds 1 and 2 these complexes are located on centers of inversion, whereas in compound 3, they occupy general positions. In the crystal structures, the complexes are packed in such a way that cavities are formed in which the solvent mol-ecules are located. Compounds 1 and 2 are isotypic, which is not the case for compound 3. In compounds 1 and 2 the solvate mol-ecules are disordered, whereas they are fully ordered in compound 3. Disorder is also observed for one of the 3-methyl-pyridine ligands in compound 2. Powder X-ray diffraction and IR measurements show that at room temperature all compounds decompose almost immediately into the same phase, as a result of the loss of the solvent mol-ecules.

Novel Composite of Nickel Thiocyanate‐Based All‐Inorganic Lead Bromide Perovskite Nanocrystals with Enhanced Luminescent and Stability for White Light‐Emitting Diodes

AbstractDoping of CsPbBr3 perovskite nanocrystals (PNCs) to achieve excellent material properties is accelerating due to their increasing use in optoelectronic devices. Herein, a novel composite of CsPbBr3 PNCs with nickel thiocyanate Ni(SCN)2 is reported, exhibiting stronger photoluminescence (PL) and more extended stability. The addition of Ni(SCN)2 at different molar concentrations reduces the surface trap states of the host PNCs. Therefore, the microstrain, dislocation density, PL emission linewidth, and Urbach energy decrease, resulting in an increased photoluminescence quantum yield (PLQY) from 72% to high above 90%. When stored in the ambient atmosphere for 120 days, the PLQY of doped PNCs is maintained by more than four times compared to host PNCs. A combination of 3D‐printed conversion layers containing green‐, yellow‐, and red‐emitting doped PNCs with blue light‐emitting diodes results in stable white light with superior color qualities. Hence, new composites with desired properties are developed as an alternative to conventional color phosphors.

A series of nickel(ii) thiocyanate complexes comprising various molar contents of isonicotinamide and water as ligands or co-crystallized moieties – an experimental and computational study

Crystal screening by varying isonicotinamide content added to Ni(ii) thiocyanate in water led to seven nickel complexes, whose structure and altered stoichiometries were analyzed by X-ray diffraction, NMR and IR spectroscopies, and DFT calculations.

Synthesis, Crystal Structures and Properties of Polymorphic and Isomeric Nickel(II)thiocyanate Coordination Compounds with 3‐Bromopyridine as Coligand

AbstractReaction of different molar ratios of Ni(NCS)2 and 3‐bromopyridine in water, methanol or acetonitrile leads to the formation of two polymorphs of composition Ni(NCS)2(3‐bromopyridine)4 (1‐I and 1‐II), as well as Ni(NCS)2(3‐bromopyridine)2(H2O)2 (2), Ni(NCS)2(3‐Bromopyridine)2(CH3OH)2 (3), Ni(NCS)2(3‐bromopyridine)2 ⋅ CH3CN (4) and Ni(NCS)2(3‐bromopyridine)2 (5). Compounds 1‐I, 1‐II, 2 and 3 consist of discrete octahedral complexes with terminal N‐bonded anionic ligands. In compound 4 the Ni cations are cis‐cis‐trans coordinated and linked into corrugated chains by pairs of μ‐1,3‐bridging thiocyanate anions. Solvent mediated conversion experiments prove that form 1‐I represents the thermodynamically stable polymorph at room temperature. TG‐DTA measurements reveal that upon heating compounds 1‐I, 1‐II, 2 and 3 lose their coligands stepwise and transform into the new crystalline phase 5 that can also be obtained from solution if the reaction is performed in n‐butanol. If the acetonitrile solvate molecules are removed from compound 4, it also transforms into 5. DC magnetic measurements for compound 4 show a maximum, which is indicative for antiferromagnetic ordering, whereas for compound 5 no magnetic ordering is observed. For both compounds, the ferromagnetic exchange constants were determined.

ЭКСТРАКЦИЯ ХЛОРИДНЫХ И ТИОЦИАНАТНЫХ АЦИДОКОМПЛЕКСОВ МЕТАЛЛОВ В СИСТЕМАХ ВЫСАЛИВАТЕЛЬ – МОНОАЛКИЛПОЛИЭТИЛЕНГЛИКОЛЬ – ВОДА

Distribution of iron (III), thallium (III, gallium, titanium (IV) chloride complexes in sodium chloride – synthanol DS-10 – water and ammonium sulfate – synthanol DS-10 – water systems, as well as iron (III), cobalt , nickel, cadmium and copper (II) thiocyanate complexes in the ammonium sulfate – synthanol DS-10 – water system investigated. It was found that the main influence on extraction is exerted by solution acidity and nature of the salting-out agent. The conditions for quantitative extraction of thallium (III) and gallium in the form of chloride complexes, as well as the conditions for maximum extraction of iron (III), zinc and cobalt thiocyanate complexes are established.

Strengthening the Magnetic Interactions in Pseudobinary First-Row Transition Metal Thiocyanates, M(NCS)2.

Understanding the effect of chemical composition on the strength of magnetic interactions is key to the design of magnets with high operating temperatures. The magnetic divalent first-row transition metal (TM) thiocyanates are a class of chemically simple layered molecular frameworks. Here, we report two new members of the family, manganese(II) thiocyanate, Mn(NCS)2, and iron(II) thiocyanate, Fe(NCS)2. Using magnetic susceptibility measurements on these materials and on cobalt(II) thiocyanate and nickel(II) thiocyanate, Co(NCS)2 and Ni(NCS)2, respectively, we identify significantly stronger net antiferromagnetic interactions between the earlier TM ions-a decrease in the Weiss constant, θ, from 29 K for Ni(NCS)2 to -115 K for Mn(NCS)2-a consequence of more diffuse 3d orbitals, increased orbital overlap, and increasing numbers of unpaired t2g electrons. We elucidate the magnetic structures of these materials: Mn(NCS)2, Fe(NCS)2, and Co(NCS)2 order into the same antiferromagnetic commensurate ground state, while Ni(NCS)2 adopts a ground state structure consisting of ferromagnetically ordered layers stacked antiferromagnetically. We show that significantly stronger exchange interactions can be realized in these thiocyanate frameworks by using earlier TMs.

An indication of spin-transition accompanied by an order-disorder structural transformation in [Ni(phpyNO)2(NCS)2] (phpyNO = tert-butyl 5-phenyl-2-pyridyl nitroxide).

Reaction of nickel(ii) thiocyanate and tert-butyl 5-phenyl-2-pyridyl nitroxide (phpyNO) afforded a 2p–3d–2p heterospin triad [Ni(phpyNO)2(NCS)2]. The compound crystallizes in the orthorhombic Pbcn space group. The whole molecule is crystallographically independent. The torsion angles around Ni–O–N–C2py are 26.8(4) and 27.3(4)° at 400 K, indicating appreciable orbital overlaps of the radical π* and nickel(ii) 3dx2−y2/3dz2 orbitals. In a low-temperature region, the torsion was enhanced, and the space group changed to monoclinic P21/c with a doubled asymmetric unit volume. The χmT value was practically null below ca. 140 K and, on heating to 400 K, gradually increased and reached 1.30 cm3 K mol−1. A van't Hoff analysis suggests a spin transition at T1/2 = 530(20) K. Density functional theory calculation reproduced ground Stotal = 0 with singlet-triplet gaps of 910 and 1263 K for the 140 K structure, and the gap was reduced to 297 K at 400 K. Consequently, the present compound can be considered as an incomplete spin-crossover material, as a result of T1/2 located above the experimental temperature window.

Synthesis of isomorphous cobalt and nickel thiocyanate coordination compounds: Effect of metals on compound properties

The reaction of 2-methylpiperazine with the thiocyanate ligand and two transition metals leads to the production of two new isomorphous [ML2SCN4] where L is the 2-methylpiperazine and [M = Co (1), and Ni (2)], presenting an octahedral configuration. These compounds were characterized by single crystal X-ray crystallography, TG-DTA analysis, as well as infrared and UV–Vis spectroscopy and TG-DTA. The magnetic and antibacterial properties were also determined. Through the link with N–H⋯S hydrogen bonds, a global 3D network was established. The studied compounds show the metal center’s impact leading to different properties. Indeed, the first compound shows high spin orbit coupling, whereas the second one shows a weak antiferromagnetic interaction. The antibacterial activity is enhanced for the cobalt compound compared with the nickel compound and the DTA/TG curves show a phase transition for the nickel compound.

Introduction to the dynamic self-organization of chemical systems

Following the presentation of basic concepts of nonlinear dynamics in chemistry in Part I, such dynamic instabilities like the oscillations, multistability, and spatiotemporal pattern formation are described in the present Part II for several real chemical systems, together with relevant kinetic models. Homogeneous systems include one of the Orban oscillators, involving catalytic oxidation of thiocyanates with hydrogen peroxide and the classical Belousov–Zhabotinsky reaction, together with its well-established Oregonator kinetic model. A heterogeneous electrochemical system involving the electroreduction of nickel thiocyanate complexes reveals bistability and oscillations interrelated as in the Boissonade–De Kepper model. Spatiotemporal patterns emerging due to the coupling between the chemical reaction and diffusion are shown based on: (1) the Belousov–Zhabotinsky reaction including its excitable characteristics, (2) the Brusselator as a source of the model Turing patterns also reported experimentally, and (3) periodic precipitation known as the Liesegang phenomena. Furthermore, the recently reported patterns formed in the systems subject to inhomogeneous temperature distribution were described. The self-organized nature of convection was shown based on both the classical Benard experiment and the convection driven electrochemically, including the “beating mercury heart” and the electrohydrodynamic formation of luminescent patterns. The course is completed with the brief description of the concept of deterministic chaos and the principle of its control as the modern subject of nonlinear dynamics. The appendix includes laboratory prescriptions for the most attractive experiments.

Two new hetero-dinuclear nickel(II)/zinc(II) complexes with compartmental Schiff bases: Synthesis, characterization and self assembly

Two compartmental Schiff bases, H2L1 [N,N′-bis(3-methoxysalicylidene)propane-1,3-diamine] and H2L2 [N,N′-bis(3-methoxysalicylidene)-2,2-dimethylpropane-1,3-diamine], have been utilized to prepare two hetero-dinuclear nickel(II)/zinc(II) complexes, [(DMSO)2NiL1Zn(NCS)2] (1) and [(DMSO)2NiL2Zn(NCS)2] (2). Both complexes have been characterized by elemental and spectral analysis. Single crystal X-ray diffraction analysis has confirmed their structures. The key step in the synthesis of these complexes is to use nickel(II) thiocyanate tetrahydrate and zinc(II) acetate dihydrate in a single pot. In each complex, octahedral nickel(II) is placed in the inner N2O2 compartment (with DMSO molecules being coordinated in the axial sites) and tetrahedral zinc(II) is placed in the outer O4 compartment of the Schiff bases. Supramolecular interactions in both complexes were explored. Both complexes show photoluminescence in DMSO solution at room temperature upon the irradiation of ultraviolet light. The life times of the excited states are in the range of 4–5ns.

Studies on the electrical, linear and nonlinear optical properties of nickel thiocyanate (NTC) , an efficient NLO crystal

Studies on the electrical, linear and nonlinear optical properties of nickel thiocyanate (NTC) , an efficient NLO crystal

Synthesis, Structures, Polymorphism, and Magnetic Properties of Transition Metal Thiocyanato Coordination Compounds

Reaction of manganese, iron, and nickel thiocyanate with 4-ethylpyridine leads to the formation of single crystals of compounds with composition M(NCS)2(L)4 (1), M(NCS)2(L)2(H2O)2 (2-Mn), and M(NCS)2(L)2 (3) with M = Mn, Fe, and Ni and L = 4-ethylpyridine. For most compounds, different polymorphic modifications are observed, and their transition behavior and thermodynamic stability was investigated. Additionally, compounds of composition M(NCS)2(L)2 (M = Mn or Ni) were prepared from solution and by thermal decomposition of compounds 1 and 2, which lead to different stable and metastable modifications. The crystal structures of most compounds were determined by single crystal X-ray diffraction and some of them by Rietveld refinements. Compounds 1 and 2 consist of octahedrally coordinated discrete complexes with terminal N-bonded thiocyanato anions. In compounds 3, the metal cations are linked by pairs of μ-1,3-bridging thiocyanato anions into chains. Surprisingly, thermal decomposition of Ni(NCS)2(4-ethylpyridine)4 leads to the formation of a new compound of composition Ni(NCS)2(4-ethylpyridine) (4-Ni). Magnetic measurements reveal that 3-Mn/II and 3-Mn/III show antiferromagnetic ordering at TN = 21.5 and 23.9 K and that 4-Ni is a metamagnet with a critical field of 1.4 kOe at 2 K. All other compounds show Curie or Curie–Weiss behavior with no magnetic anomalies.

Synthesis and Characterization of New 2D Coordination Polymers based on Mn(NCS)2 and Ni(NCS)2 with 1, 2‐Bis(4‐pyridyl)‐ethane as Co‐Ligand

AbstractReaction of manganese(II) and nickel(II) thiocyanate with 1, 2‐bis(4‐pyridyl)‐ethane (bpa) leads to the formation of literature known compounds of composition M(NCS)2(bpa)2 with M = Mn (1‐Mn) and Ni (1‐Ni). On heating 1‐Mn and 1‐Ni transform into new compounds of composition M(NCS)2(bpa) with M = Mn (2‐Mn) and Ni (2‐Ni). These compounds can also be prepared in solution. In both synthetic routes only microcrystalline powders are obtained with crystals too small for single‐crystal X‐ray diffraction. Therefore, the structures of both compounds were solved and refined from X‐ray powder data. In the crystal structure the transition metal cations are coordinated by two bpa co‐ligands and four thiocyanato anions within slightly distorted octahedra. The metal cations are linked by μ‐1, 3‐bridging thiocyanato anions into chains, that are further connected into layers by the bpa ligands. Magnetic measurements on 2‐Ni shows only Curie‐Weiss paramagnetism. In contrast, for 2‐Mn an antiferromagnetic ordering is observed but on further cooling the susceptibility curves increase indicating for canted antiferromagnetism. Further measurements prove that the increase at lower temperatures can be traced back to a small contamination with 1‐Mn, which is always present independent if this compound is prepared by thermal decomposition or by crystallization from solution. In the course of the crystallization experiments a few single crystals of two additional compounds of composition Mn(NCS)2(bpa)(H2O)2 (3‐Mn) and [Mn(NCS)2]2(bpa)3(CH3OH)2 (4‐Mn) were accidently obtained and characterized by single crystal structure analysis. The results of the magnetic measurements are compared with those for related compounds with different neutral N‐donor ligands.

Improved synthesis of a trisphosphine ligand and crystallographic characterization of the ligand and nickel thiocyanate complex

Improved syntheses of o-C6H4(PEt2)(X) (X=F, Br, I) and the trisphosphine PhP[o-C6H4(PEt2)]2 have been developed and are applicable to a wide variety of phosphine substituents. The trisphosphine, PhP(o-Ph–PEt2)2, has been fully characterized spectroscopically and, for the first time, crystallographically. Reaction of the P3 ligand with one equivalent of NiCl2 or Ni(BF4)2 followed by 2.5 equivalents of KNCS produces the monometallic complexes Ni(X)2[κ3-PhP(o-Ph–PEt2)2], (X=Cl or NCS). The nickel thiocyanate complex has been characterized via a crystal structure. The nickel center has a square pyramidal structure with one of the NCS ligands occupying the apical coordination site. The Ni complex crystallizes in the P1¯ space group with an unusual six molecules in the asymmetric unit (Z′=6), and twelve in the unit cell.

New cobalt and nickel thiocyanato coordination polymers with pyridazine: Synthesis, structure and desolvation/resolvation behavior

Reaction of cobalt(II) thiocyanate and pyridazine in water under hydrothermal conditions leads to the formation of [Co2(NCS)4(pyridazine)2(H2O)]n (1-Co), whereas the reaction of nickel(II) thiocyanate with pyridazine in methanol under similar conditions results in the formation of [Ni2(NCS)4(pyridazine)2(CH3OH)]n (1-Ni). In their crystal structure the metal cations are linked via μ-1,3- and μ-1,1-thiocyanato anions as well as bridging pyridazine ligands into chains, which are further connected into layers by O–H⋯S hydrogen bonding. Investigations on the thermal behavior show that in both compounds the solvent molecules can be removed, which lead to the formation of compounds of composition [M2(NCS)4(pyridazine)2]n (M=cobalt, 2-Co; nickel, 2-Ni). XRPD investigations indicate that both compounds are isotypic and IR spectroscopic investigations indicate that a more condensed thiocyanato network has formed. On rehydration 2-Co and 2-Ni retransforms into hydrates, which are isotypic and which exhibits powder patterns different from those of 1-Co and 1-Ni. If 2-Co and 2-Ni a stored in a methanol atmosphere an unknown crystalline phase is formed for 2-Ni, whereas the cobalt compound transforms into the methanol solvate [Co3(NCS)6(pyridazine)2]·(CH3OH)2 known in literature. Magnetic measurements reveal that compounds 1-Co and 1-Ni shows an antiferromagnetic ordering at TN=9.6 and 4.7K.

Tetrakis(pyridazine-κN)bis(thiocyanato-κN)nickel(II) pyridazine disolvate

The reaction of nickel(II) thio­cyanate with an excess of pyridazine leads to single crystals of the title compound, [Ni(NCS)2(C4H4N2)4]·2C4H4N2. The NiII cations are coordinated by two terminal N-bonded thio­cyanate anions (trans) and four pyridazine ligands in a slightly distorted octa­hedral geometry. The discrete complexes are arranged into layers parallel to the ab plane which are separated by additional non-coordinated pyridazine ligands.

Discussion of Planarity of Molecular Structures Using Novel Pentanuclear Cu/Ni Complexes as an Example

Two novel heterometallic complexes, [Cu2Ni3(NCS)4(Me2Ea)6] (1) and [Cu2Ni3Cl4(Me2Ea)6] (2) (HMe2Ea = 2-dimethylaminoethanol), have been prepared using a one-pot reaction of copper powder with nickel thiocyanate (1) or chloride (2) in an acetonitrile solution of HMe2Ea in air. The magnetic investigations disclose dominant ferromagnetic exchange interactions with S = 4 and 2 ground states for 1 and 2, respectively. A planar arrangement of five metal centers in both compounds inspired us to study the question of planarity of polynuclear coordination compounds having MaXb cores (where M = metal and X = bridging atom). The distribution, obtained by the searches via the Cambridge Structural Database, of the structures possessing a planar disposition of the metal centers, depending on their nuclearity, is discussed, and typical planar molecular structure types (MST) are identified. It is demonstrated that the relative amounts of planar structures obey exponential decay in the 3–8 nuclearity region, with the exce...

Synthesis, Structures, and Thermal and Magnetic Properties of New Coordination Polymers Based on Mn(II) and Ni(II) Thiocyanato Complexes with trans-1,2-Bis(4-pyridyl)ethylene as Ligand

Hydrothermal reaction of manganese(II) thiocyanate with trans-1,2-bis(4-pyridyl)ethylene (bpe) in water leads to the formation of the new ligand-rich 1 : 3 (ratio metal/ligand) compound [Mn(NCS)2- (bpe)2・(bpe)] (1-Mn). In the crystal structure the manganese cations are octahedrally coordinated by two thiocyanato anions and four bpe ligands and are linked into layers by the bpe ligands. Reaction of manganese(II) thiocyanate with bpe in water leads to the known 1 : 2 compound Mn(NCS)2- (bpe)2(H2O)2 (2-Mn). On heating compound 1-Mn is transformed directly into a ligand-deficient 1 : 1 compound of composition [Mn(NCS)2(bpe)]n (4-Mn), whereas on thermal decomposition of 2-Mn a new 1 : 2 anhydrate of composition [Mn(NCS)2(bpe)2]n (3-Mn) can be isolated in the first step, which is transformed into 4-Mn on further heating. In further experiments single crystals of the ligand-deficient compound 4-Mn were also obtained. In its crystal structure the manganese cations are connected by the thiocyanato anions into Mn-(NCS)2-Mn double chains, which are further connected by bpe ligands into layers. In contrast, reaction of nickel(II) thiocyanate with bpe leads always to the formation of only one crystalline phase (1-Ni) that is isotypic to 4-Mn. Magnetic measurements have revealed that all compounds show Curie or Curie-Weiss paramagnetism.