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Crystal structure of [{[Ni(C10H24N4)][Ni(CN)4]}·2H2O]n, a one-dimensional coordination polymer formed from the [Ni(cyclam)]2+ cation and the [Ni(CN)4]2– anion

ABSTRACT: The title coordination polymer consists of parallel linear chains built up of macrocyclic cations possessing a slightly tetragonally distorted NiN6 octahedral coordination geometry formed by four N atoms of the azamacrocyclic ligand in the equatorial plane and two trans N atoms of the cyanide groups of the bridging tetracyanonickelate anion in the axial positions. In the crystal, two independent [1 The asymmetric unit of the title compound, catena-poly[[[(1,4,8,11-tetraazacyclotetradecane-κ4N1,N4,N8,N11)nickel(II)]-μ-cyanido-κ2N:C-[bis(cyanido-κC)nickel(II)]-μ-cyanido-κ2C:N] dihydrate], {[Ni2(CN)4(C10H24N4)]·2H2O]n or [{[Ni(C10H24N4)][Ni(CN)4]}·2H2O]n, consists of a pair of crystallographically non-equivalent macrocyclic cations and anions. The nickel(II) ions (all with site symmetry

SUBMITTER: Tsymbal L

PROVIDER: S-EPMC8587981 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Crystal Engineering and Photomagnetic Studies of CN-Bridged Coordination Polymers Based on Octacyanidometallates(IV) and [Ni(cyclam)]2.

Project description:A series of new CN-bridged coordination networks of different dimensionality and topology was obtained through the modification of reaction conditions between [Ni(cyclam)]2+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) and [W(CN)8]4-. The factors determining the reaction pathway are temperature and addition of the LiCl electrolyte. The products include three negatively charged frameworks incorporating Li+ guests: the 1D Li2[Ni(cyclam)][W(CN)8]·6H2O (1) straight chain, the 1D Li2[Ni(cyclam)][W(CN)8]·2H2O (2) zigzag chain, and the 2D Li2[Ni(cyclam)]3[W(CN)8]2·24H2O (3) honeycomb-like network, as well as the 3D two-fold interpenetrating [Ni(cyclam)]5[Ni(CN)4][W(CN)8]2·11H2O (4) network and the 1D [Ni(cyclam)][Ni(CN)4]·2H2O (5) chain, which result from partial decomposition of the starting complexes. Together with the previously characterized 3D [Ni(cyclam)]2[W(CN)8]·16H2O (6) network, they constitute the largest family of CN-bridged coordination polymers obtained from the same pair of building blocks. All compounds exhibit paramagnetic behavior because of the separation of paramagnetic nickel(II) centers through the diamagnetic polycyanidometallates. However, the presence of the photomagnetically active octacyanidotungstate(IV) ions allowed observation of the magnetic superexchange after the violet light excitation (405 nm) for compound 3, which constitutes the first example of the photomagnetic effect in a NiII-[WIV(CN)8] system. The photomagnetic investigations for fully hydrated and dehydrated sample of 3, as well as for the isostructural octacyanidomolybdate(IV)-based network are discussed.

| S-EPMC9455600 | biostudies-literature

New Photosensitizers Based on Heteroleptic CuI Complexes and CO2 Photocatalytic Reduction with [NiII (cyclam)]Cl2.

Project description:Earth-abundant metal complexes have been attracting increasing attention in the field of photo(redox)catalysis. In this work, the synthesis and full characterisation of four new heteroleptic CuI complexes are reported, which can work as photosensitizers. The complexes bear a bulky diphosphine (DPEPhos=bis[(2-diphenylphosphino)phenyl] ether) and a diimine chelating ligand based on 1-benzyl-4-(quinol-2'yl)-1,2,3-triazole. Their absorption has a relative maximum in the visible-light region, up to 450 nm. Thus, their use in photocatalytic systems for the reduction of CO2 with blue light in combination with the known catalyst [NiII (cyclam)]Cl2 was tested. This system produced CO as the main product through visible light (λ=420 nm) with a TON up to 8 after 4 hours. This value is in line with other photocatalytic systems using the same catalyst. Nevertheless, this system is entirely noble-metal free.

| S-EPMC7497214 | biostudies-literature

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Crystal structure of the one-dimensional coordination polymer formed by the macrocyclic [Ni(cyclam)]2+ cation and the dianion of di-phenyl-silanediylbis(4-benzoic acid).

Project description:The asymmetric unit of the title compound, catena-poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-?4 N 1,N 4,N 8,N 11)nickel(II)]-?-4,4'-(di-phenyl-silanedi-yl)dibenz-o-ato-?2 O:O'] sesquihydrate], {[Ni(C26H18O4Si)(C10H24N4)]·1.5H2O} n , consists of the halves of the centrosymmetric macrocyclic cation and the C 2-symmetric di-carboxyl-ate dianion and of the water mol-ecule of crystallization. The Ni2+ ion is coordinated by the four secondary N atoms of the macrocyclic ligand characterized by the most energetically favourable trans-III conformation and two mutually trans O atoms of the carboxyl-ate, forming a slightly tetra-gonally elongated trans-N4O2 octa-hedron. The crystals are composed of parallel polymeric chains of the macrocyclic cations linked by the anions of the acid running along the [101] direction. Each polymeric chain is bonded to four neighbouring ones via water mol-ecules providing O-H?O hydrogen bonds to the non-coordinated carboxyl O atoms to form a three-dimensional supra-molecular network.

| S-EPMC7274011 | biostudies-literature

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2 )3 ]- , Stabilized by a Weakly Coordinating Cation.

Project description:The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH2 )3 ]- salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water-stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene-base-catalyzed preparation of the Ruppert-Prakash reagent Me3 SiCF3 using fluoroform (HCF3 ) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.

| S-EPMC6790940 | biostudies-literature

?-Noninnocence: Masked Phenyl-Cation Transfer at Formal NiIV.

Project description:Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of -2 at a transition-metal center. For a series of formal high-valent NiIV complexes, aryl-CF3 bond-forming reductive elimination was reported to occur readily (Bour et?al. J. Am. Chem. Soc. 2015, 137, 8034-8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal NiIV centers are better described as approaching a +II oxidation state, originating from highly covalent metal-ligand bonds, a phenomenon attributable to ?-noninnocence. A direct consequence is that the elimination of aryl-CF3 products occurs in an essentially redox-neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF3 group is transferred to an electrophilic aryl group. The uncovered role of ?-noninnocence in metal-ligand bonding, and of an essentially redox-neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry.

| S-EPMC6771483 | biostudies-literature

Ternary Heterostructural Pt/CNx/Ni as a Supercatalyst for Oxygen Reduction.

Project description:We report here a supercatalyst for oxygen reduction of Pt/CNx/Ni in a unique ternary heterostructure, in which the Pt and the underlying Ni nanoparticles are separated by two to three layers of nitrogen-doped carbon (CNx), which mediates the transfer of electrons from the inner Ni to the outer Pt and protects the Ni against corrosion at the same time. The well-engineered low-Pt catalyst shows ∼780% enhanced specific mass activity or 490% enhanced specific surface activity compared with a commercial Pt/C catalyst toward oxygen reduction. More importantly, the exceptionally strong tune on the Pt by the unique structure makes the catalyst superbly stable, and its mass activity of 0.72 A/mgPt at 0.90 V (well above the US Department of Energy's 2020 target of 0.44 A/mgPt at 0.90 V) after 50,000 cyclic voltammetry cycles under acidic conditions is still better than that of the fresh commercial catalyst.

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Crystal structure of [K(18-crown-6)]+ 2[Pt(CN)4]2.

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| S-EPMC9635596 | biostudies-literature

Phase segregated Cu2-x Se/Ni3Se4 bimetallic selenide nanocrystals formed through the cation exchange reaction for active water oxidation precatalysts.

Project description:Control over the composition and nanostructure of solid electrocatalysts is quite important for drastic improvement of their performance. The cation exchange reaction of nanocrystals (NCs) has been reported as the way to provide metastable crystal structures and complicated functional nanostructures that are not accessible by conventional synthetic methods. Herein we demonstrate the cation exchange-derived formation of metastable spinel Ni3Se4 NCs (sp-Ni3Se4) and phase segregated berzelianite Cu2-x Se (ber-Cu2-x Se)/sp-Ni3Se4 heterostructured NCs as active oxygen evolution reaction (OER) catalysts. A rare sp-Ni3Se4 phase was formed by cation exchange of ber-Cu2-x Se NCs with Ni2+ ions, because both phases have the face-centered cubic (fcc) Se anion sublattice. Tuning the Ni : Cu molar ratio leads to the formation of Janus-type ber-Cu2-x Se/sp-Ni3Se4 heterostructured NCs. The NCs of sp-Ni3Se4 and ber-Cu2-x Se/sp-Ni3Se4 heterostructures exhibited high catalytic activities in the OER with small overpotentials of 250 and 230 mV at 10 mA cm-2 in 0.1 M KOH, respectively. They were electrochemically oxidized during the OER to give hydroxides as the real active species. We anticipate that the cation exchange reaction could have enormous potential for the creation of novel heterostructured NCs showing superior catalytic performance.

| S-EPMC8148079 | biostudies-literature

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