Weak Antiferromagnetic Interactions Research Articles

Copper bromide complexes with triethylbenzylammonium (TEBA): the ladder complex (TEBA)2Cu2Br6, the polymorph dimer α-(TEBA)2Cu2Br6, and the monomeric salt (TEBA)2CuBr4

Two new complexes of copper(II) with bromide ligands and triethylbenzylammonium (TEBA) cations are reported, α-(TEBA)2[Cu2Br6] (1), and (TEBA)2[CuBr4] (2). The syntheses, crystal structures, and magnetic properties are described. 1 crystallizes as bibromide bridged dimers which are linked into square layers via short Br…Br contacts. Variable temperature magnetic susceptibility data indicate ferromagnetic interactions within the dimers (J/kB = 107(4) K) with weak interdimer antiferromagnetic interactions (θ = −3.47(6) K). 2 crystallizes as discrete tetrabromidocuprate anions which are well isolated by the bulk of the TEBA cations. Magnetic susceptibility measurements indicate negligible magnetic interactions in the material. The magnetic properties of the known polymorph (TEBA)2[Cu2Br6] (3) were reexamined in light of the properties of 1 and suggest a significantly stronger interaction within the dimer (J/kB ∼ 110(4) K) than originally proposed. These findings are in agreement considering the nearly identical structures of the Cu2Br6 2- dimers in 1 and 3.

An Open-Shell Functionalization of Inorganic Benzene.

A borazine derivative functionalized by nitroxide free radicals, N,N',N″-(tris(4-Bromophenyl))-B,B',B″-tris((2,6-dimethyl-4-(N-tert-butyl-N-oxyamino)phenyl) borazine (TriBNit), was synthesized as a milestone of open-shell inorganic benzene. The crystal structure determined from X-ray diffraction on a single crystal ascertains the grafting of three nitroxide radicals. The temperature dependence of the magnetic susceptibility evidences weak intramolecular antiferromagnetic interactions between the radicals with strong intermolecular antiferromagnetic interactions between two nitroxide moieties of two neighboring molecules. EPR spectroscopy at 80 K on a frozen glassy solution evidences the coexistence of S = 1/2 and S = 3/2 ground-spin state species. This is ascribed to the nitroxide radicals having different orientations with respect to the borazine core giving rise either to antiferromagnetic interaction with a low ground-spin state S = 1/2 or to ferromagnetic interaction with a high ground-spin state S = 3/2 as supported by theoretical data. At room temperature, because of nitroxide mobility, the EPR spectrum is averaged to a ground-spin state S = 1/2.

Solvent-induced SC-SC transformation between 3D and 1D Co-MOFs: Fluorescence sensing and magnetic properties

By utilizing an aromatic π-conjugated organic ligand as a linker, we successfully synthesized two new coordination complexes, namely, a three-dimensional framework (3D) [Co(DCPA)(DMA)(H2O)] (Co-MOF-1) and a one-dimensional chain (1D) [Co(DCPA)(H2O)4]·4H2O (Co-MOF-2) (DCPA = 9, 10-di (p-carboxyphenyl) anthracene). Both complexes were determined by single crystal X-ray diffraction analysis, Thermogravimetric analysis, PXRD, XPS, UV–vis and IR spectrum, etc. Interestingly, the reversibly single-crystal-to-single-crystal (SC-SC) structural transformation between the 3D framework and 1D chain structures could be achieved successfully by controlling the stimulation of external temperature and solvent. Besides, a series of fluorescence sensing experiments were carried out for Co-MOF-1, demonstrating excellent selective and sensitive “turn-on” towards Al3+, Cr3+, Amoxicillin (AMX), and 4,5-Imidazoledicarbonitrile (DCI), especially Al3+ and AMX. Moreover, the detection mechanism was also further investigated. In addition, the magnetic studies indicated that Co-MOF-1 and Co-MOF-2 have weak antiferromagnetic interaction. The current research elucidates different structural variations exhibited by cobalt-containing compounds in extended framework architectures and properties.

Synthesis, characterization and magnetic properties of a hexanuclear copper (II) complex with hydroxido, alkoxido and phenoxido bridges

A new CuII6 complex, formulated as [Cu6(L)3(µ3-OH)(H2O)(OH)(NO3)]·2H2O·7CH3OH (1) has been prepared using the symmetrical N2O3-donor Schiff-base ligand H3L = N,N′-(2-hydroxypropane-1,3-diyl)bis(2-hydroxyacetophenimine). Compound 1 has been structurally and spectroscopically characterized. Single crystal X-ray diffraction analysis reveals that 1 crystallizes in the triclinic space group P-1 and consists of a CuII6 complex where each deprotonated ligand chelates two CuII centres. Three of the six independent CuII centres are arranged in an almost equilateral triangle with double Cu-O-Cu bridges, formed by a μ3-hydroxido and phenoxido bridges. Each of the three CuII centres in the triangle is further connected to one CuII centre through a single alkoxido bridge. The magnetic properties indicate the presence of moderate and weak antiferromagnetic interactions through the double and single oxido bridges, respectively.

Chloride bibridged Cu(II) chains with n-Br-2-pyridone molecules

The compounds catena-[diaquadichloridocopper(II)] bis(4-bromo-2-pyridone) (1) and catena-[bis(5-bromo-2-pyridone)dichloridocopper(II)] (2) have been prepared and characterized crystallographically. Both show bichloride bridged chains of Cu(II) ions with coordinated water molecules in the axial sites for 1 and coordinated 5-bromo-2-pyridone molecules in the axial sites for 2. 1 incorporates two 4-bromo-2-pyridone molecules co-crystallized in the lattice. Variable temperature magnetic susceptibility measurements for 1 indicate the presence of weak antiferromagnetic interactions [J/kB = −7.06(5) K] similar to copper(II) chloride dihydrate, but without that compound’s significant inter-chain interactions and Néel transition.

Structural and Magnetic Properties of Dimeric Capsule Assemblies Formed by Cyclic Trinuclear Complexes.

Cyclic trinuclear homo-metal complexes, [{Fe(L3+2Br)py}3] (1) and [{Mn(L3+2Br)}3(py)2 MeOH] (2), along with a hetero-metal complex, [FeMn2(L3+2H)3(DMF)3] (3), were synthesized using asymmetric ditopic ligands (H3L3+2H: 2-(2-hydroxyphenyl)-6-ol-5-(salicylideneamino)benzoxazole, H3L3+2Br: 2-(2-hydrox-5-bromoyphenyl)-6-ol-5-(5-bromosalicylideneamino)benzoxazole). The molecular structure of 1 is characterized by a tripod structure with three-fold symmetry, where an enantiomer pair forms a dimeric capsule with dimensions of approximately 3 × 1.6 × 1.6 nm3. Complexes 2 and 3, which lack three-fold symmetry, exhibit similar molecular structures to previously reported complexes with these ligands, but do not form a capsule structure. Magnetic measurements of 1-3 reveal the presence of significantly weak antiferromagnetic interactions between the metal ions.

Investigation of the electronic, optical and magnetic properties of a novel two-dimensional lead-free perovskite: High visible-light absorption and long-range magnetic ordering.

Recently, big issues that need to be solved in photovoltaic solar cells area are the toxicity and instability of lead halide perovskites which have shown exceptional photoelectric performances. Herein, we report the synthesis and physico-chemical characterization of a novel two-dimensional (2D) lead-free perovskite. The 2D Cu(II)-based perovskite (C4N3H16)[CuCl4]∙Cl was successfully stabilized by the slow evaporation method under room temperature. The X-ray diffraction shows a layered structure with an inorganic network formed by four corners sharing CuCl6 octahedra. The UV-Vis absorption analysis confirms the manifestation of the cooperative Jahn-Teller effect around the Cu(II) ions. In addition to the ligand-to-metal charge transfer transitions, crystal field transitions (d-d) enhance the visible-light absorbance and make the material suitable for green solar cell applications with a band gap energy of 2.17 eV. The thermal analysis revealed the thermal stability of (C4N3H16)[CuCl4]∙Cl. Magnetic measurements revealed the presence of dominant ferromagnetic exchange interactions with J/kB = 22.85 K within the 2d planes, with a weak antiferromagnetic exchange interaction yielding a long-range magnetic ordering at 12 K.

Copper (II) halide compounds with cationic N-donor ligands: Design, synthesis, structure and magnetism

Copper (II) complexes of the cationic ligands 1-(4′-pyridyl)-pyridinium (L1) and 1-(4′-pyridyl)-pyridin-4-ol (L2) have been prepared and characterized by single crystal X-ray diffraction and variable temperature magnetic susceptibility measurements: [Cu(L1)2X2]X2 [where X = Cl (1), Br (2)], and [Cu(L2)2X2]X2 [where X = Cl (3), Br (4)]. The complexes are fundamentally square planar with L2X2 coordination planes and long, semi-coordinate bonds to the additional halide ions. All compounds crystallize in monoclinic systems with 1 and 2 in the P21/n space group and 3 and 4 in the P21/c space group. The crystal structures are stabilized by both non-classical (in the case of 1 and 2) and classical (3 and 4) hydrogen bonds. EPR data for 1–4 support a rhombohedral structure, in good agreement with the local geometry as seen in the crystal structures. Magnetic susceptibility measurements show the presence of very weak antiferromagnetic interactions. In addition, the syntheses and magnetic properties of two neutral complexes, [Cu(L3)2X2]·2H2O [L3 = 1-(4′-pyridino)-4-pyridone; X = Cl (5), Br (6)] are reported. Magnetic susceptibility data indicate the presence of moderate antiferromagnetic exchange interactions [J ∼ 28 K (5), 60 K (6)] which were well modeled by the S = 1/2 Heisenberg uniform chain model.

Synthesis, characterization and study of magnetic property of two isomorphic Cu(II) coordination polymers (CP) with chromone based ligand systems

Synthesis, characterization and magnetic properties of two Cu(II)-based coordination polymers (CPs, [{Cu(L1)(N(CN)2)}(ClO4)]n L1 = 3-(((2-(diethylamino)ethyl)imino)methyl)-4H-chromen-4-one (1) and [{Cu(L2)(N(CN)2)}(ClO4)]n L2 = 3-(((2-(dimethylamino)ethyl)imino)methyl)-4H-chromen-4-one (2)) involving chromone based chelating ligands and dicyanamide bridging ligands are reported. Both compounds have been characterized by physicochemical methods and the crystal structures have been determined by X-ray diffraction analysis, disclosing that they are isostructural and isomorphous compounds of polymeric linear chains where the central metal has adopted distorted square pyramidal coordination geometry. The magnetic studies reveal that the synthesized compounds show a prevailing paramagnetic behavior. Only below 15 K does a weak antiferromagnetic interaction become effective in these systems, and they have been further analyzed and interpreted.

Low-temperature magnetism of Ln2Ba (Ln = Nd, Er, Ho) furoate-based polymeric chains: Slow relaxation, magnetic anisotropy and interactions

The synthesis, structure and magnetothermal properties of three new lanthanide 1D polymeric complexes, {[Ln2Ba(α-fur)8(H2O)4]}n for Ln = Nd (1), Er (2) and {[Ho2Ba(α-fur)8(H2O)4]⋅2H2O}n (3), based on carboxylic α-fur = C4H3OCOO ligands is reported. The α-furoate ligands consolidate zigzag chains formed by Ln2 dimers separated by Ba ions. Ab initio calculations, in combination with the fit of experimental static magnetization and heat capacity, predict the magnetic ground state, energy levels and magnetic interactions in these heteronuclear nanomagnets. Nd2Ba (1) presents two different coordination sites for Nd, with an orthorhombic magnetic ground state. Nd ions are coupled along the chain through a weak antiferromagnetic (AF) interaction J″/kB = −0.08 K. Er(III) ions in Er2Ba (2) present a highly axial ground state, forming magnetic dimers with an interaction of J′/kB = −8.6 K, while interdimer coupling along the chain is J″/kB = −0.28 K. The Ho2Ba (3) complex consists of a highly anisotropic quasi-doublet with a ΔHo/kB = 0.7 K gap. Non-Kramers Ho ions form magnetic dimers within the Ho2Ba cluster, coupled by an AF intradimer interaction J′/kB = −2.5 K. The three complexes exhibit in-field slow relaxation of the magnetization: 1 relaxes through an Orbach process at high temperatures [Ueff/kB = 60(1) K] evolving to quantum tunneling below 3 K [τQT = 0.05(1) s]; 2 exhibits a rapid Orbach-like process [τ0 = 8(6)⋅10–8 s and Ueff/kB = 10(2) K] and 3 shows a direct process [τ = 0.4(1) s].

Antiferromagnetic resorcinol bridged dinuclear square-planar copper (II) complexes: Syntheses, structural, spectroscopic and magnetic properties

A new C2-symmetric Schiff base ligand (H2L) featuring a core resorcinol bridging unit has been created, utilizing the Duff formylation reaction followed by the Schiff base condensation reaction. The ligand was characterized by various spectroscopic techniques. Cu(II) salts with varying coordinating anions (Cl− and SCN−) in methanol were allowed to react with this ligand in a 2:1 M ratio to create dinuclear Cu(II) complexes. The complexes were isolated in pure form and characterized by, elemental analysis,single crystal X-ray crystallography and various spectroscopic techniques. X-ray analysis discloses that both complexes are dinuclear, where the ligand (H2L) being tridentate in nature, coordinates to Cu(II) through its two N donor atoms and one O donor atom in the equatorial positions. The respective anions (−Cl− for 1 and –SCN− for 2) coordinate to Cu(II) to complete its square planar geometry. Temperature dependent magnetic susceptibility measurements indicate weak antiferromagnetic exchange interactions with a coupling constant of J = −5.9(1) cm−1 and g = 2.148(1) for 1 and J = −10.08(1) cm−1 and g = 2.106(1) for 2.

Lanthanide complexes of monosubstituted Calix[4]arene-ligands: Synthesis, structures, and magnetic properties of [Ln2(L)2(MeOH)4] (Ln = La, Gd, Tb, Tm) (H3L = mono-O-propargyl-calix[4]arene)

The ability of the propargylated calix[4]arene ligand H3L (= 25-(2-propynyloxy)-26,27,28-trihydroxy-calix[4]arene) to bind lanthanide ions has been studied. The triply deprotonated ligand was found to support dinuclear neutral complexes of composition [Ln2L2(MeOH)4] (Ln= La (1), Gd (2), Tb (3), Tm (4)). Spectroscopic data for 1–4 as well as X-ray crystallographic analysis of single crystals of 1∙(MeOH)2 and 2∙(MeOH)2 reveal that two [LnL] entities dimerize via two phenolato groups to generate a centrosymmetric (MeOH)2O3Ln(μ-O)2LnO3(OHMe)2 core structure. The Ln3+ ions reside in a distorted mono-capped octahedral coordination environment. Squid magnetic measurements for the Gd3+ and Tb3+ complexes agree with the formulation as dinuclear compounds, and reveal the presence of very weak antiferromagnetic exchange interactions (J < 0.1 cm−1). The ability of the La3+ complex to react with azides in a click reaction is also demonstrated.

Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal-Organic Framework.

Two-dimensional conductive metal-organic frameworks have emerged as promising electronic materials for applications in (opto)electronic, thermoelectric, magnetic, electrocatalytic, and energy storage devices. Many bottom-up or postsynthetic protocols have been developed to isolate these materials or further modulate their electronic properties. However, some methodologies commonly used in classic semiconductors, notably, aliovalent substitution, are conspicuously absent. Here, we demonstrate how aliovalent Fe(III) to Ni(II) substitution enables the isolation of a Ni bis(dithiolene) material from a previously reported Fe analogue. Detailed characterization supports the idea that aliovalent substitution of Fe(III) to Ni(II) results in an in situ oxidation of the organic dithiolene linker. This substitution-induced redox tuning modulates the electronic properties in the system, leading to higher electrical conductivity and Hall mobility but slightly lower carrier densities and weaker antiferromagnetic interactions. Moreover, this aliovalent substitution improves the material's electrochemical stability and thus enables pseudocapacitive behavior in the Ni material. These results demonstrate how classic aliovalent substitution strategies in semiconductors can also be leveraged in conductive MOFs and add further support to this class of compounds as emerging electronic materials.

New in situ generated acylhydrazidate-coordinated complexes: Syntheses, structural characterizations and magnetic properties

The present study reports the successful synthesis of three new magnetic coordination polymers, namely [Mn(BPTH)(H2O)]n (1), [Co(BPTH)(phen)]n (2), and [Co(BPTA)(phen)(H2O)2]n (3), through a solvothermal method (H2BPTH = biphenyl-3,3′,4,4′-tetracarboxyhydrazide, H2BPTA = biphenyl-3,3′,4,4′-tetracarboxylic acid, phen = 1,10-phenanthroline). In compounds 1 and 2, the bishydrazide ligand H2BPTH is formed by in situ acylation of H2BPTA with hydrazine hydrate. All the three title compounds contain M2O2 clusters (M=Mn(1), Co(2) and Co(3)). In compound 1, the amido-oxygen atoms O1 coordinate with Mn2+ to form a Mn2O2 cluster, while the adjacent Mn2O2 cluster is interconnected by the ligand's oxygen atoms O3 and O4, resulting in an infinite expansion into a 3D network structure. Compound 2 exhibits a 1D chain structure containing Co2O2 clusters, which further extends into a 2D supramolecular layer through π···π stacking interactions. Compound 3 comprises adjacent Co2O2 clusters interconnected by oxygen atoms O1, O2, and O5 on the ligand to form a 2D layered architecture. The 2D layers are linked through intermolecular O–H···O hydrogen bonds of H2BPTA ligands to form a 3D supramolecular network. Magnetic measurements reveal weak ferromagnetic behavior for compound 1 while compounds 2 and 3 exhibit weak antiferromagnetic interactions at different temperatures. Overall, this research presents new insights into the design and synthesis of coordination polymers with diverse structures and magnetic properties.

Hydrothermal synthesis of (C5H14N2)[CoCl4]⸳0.5H2O: Crystal structure, spectroscopic characterization, thermal behavior, magnetic properties and biological evaluation

The organic-inorganic compound (C5H14N2)[CoCl4]⸳0.5H2O, I, was characterized by various physicochemical techniques. The X-ray diffraction analysis revealed that the compound crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The atomic arrangement the Co(II) complex is built from isolated [CoCl4]2– anions, 1-methylpiperazine-1,4-diium [C5H14N2]2+ cations and free water molecules. The crystal structure study showed that the cohesion of I is assured through N–H···Cl and N–H···O hydrogen bonds giving birth to a 3-D architecture. Hirshfeld surface analysis revealed that Cl···H/H···Cl and H···H (58.5 and 36.4%, respectively) are the most significant interactions between species. Minor O···H/H···O interactions are also present. The compound was characterized by thermal analysis, TGA-DTA showed the removal of the co-crystallized water before 100 °C and a first mass loss at around 120 °C. Magnetic measurements are in good agreement with isolated, S = 3/2, tetrahedral [CoCl4]2− anions. The negative Weiss constant of -1.35 indicates single-ion anisotropy and very weak antiferromagnetic interactions. UV–visible spectroscopy reveals three weak absorption bands in the visible range due to the d-d electronic transitions typical of the Co(II) tetra-coordinated. A bioassay showed antibacterial activity against the gram negative Klebsiella pneumonia and gram positive Bacillus ceureus, Listeria monocytogenes, and Micrococcus lutues.

Novel Trinuclear Copper(II) Complex: Crystal Structure at 100 K and Magnetic Properties of (R, S)-di[(6,7-dimethoxy-isoquinolin-1-yl)-(3,4-dimethoxy-phenyl)-methanolato]-tetra(2-hydroxybenzoato)-diaqua-tricopper dihydrate, [Cu3(C7H5O3)4(C20H20NO5)2(H2O)2]·2(H2O)

The crystal structure of [Cu3(C7H5O3)4(C20H20NO5)2(H2O)2]·2(H2O) (1) and analysis of temperature and field dependence of magnetic susceptibility is reported in this work. The structure of 1 is composed of trinuclear complex units and water molecules. The middle copper atom occupies the center of symmetry. N, O-bonded (6,7-dimethoxy-isoquinolin-1-yl)-(3,4-di­methoxy-phenyl)-methanolato ligands, 2-hydroxybenzoates with bridging carboxylic groups, and oxo-bridged water molecules connect the middle Cu(II) atom with the terminal copper atoms. Two 2-hydroxybenzoates coordinate the terminal copper atoms via one carboxylic oxygen and an O atom of the hydroxyl group. The analysis of copper coordination by bond-valence sum approach and relevant structural correlation is consistent with hexacoordinated Cu(II) centers. Cu···Cu separation is 3.0269(3) Å. The magnetism of 1 shows a strong ferromagnetic interaction between the neighboring metallic centers accompanied by very weak antiferromagnetic intermolecular interactions. The complex units are mutually held by π···π stack interactions of 2-hydroxybenzoates and hydrogen bonds.Graphical A new N,O bonded ligands, (R, S)-[(6,7-dimethoxy-isoquinolin-1-yl)-(3,4-dimethoxy-phenyl)-methanolate] coordinate the terminal atoms of the trinuclear copper(II) complex.

Intensity and lifetime ratiometric luminescent thermometer based on a Tb(III) coordination polymer.

A three-dimensional terbium(III) coordination polymer of formula [Tb(bttb)0.5(2,5-pzdc)0.5]n (1) [H4bttb = 1,2,4,5-tetrakis(4'-carboxyphenyl)benzene and H2-2,5-pzdc = 2,5-pyrazinedicarboxylic acid] was obtained under hydrothermal conditions. The bttb4- tetraanion in 1 adopts the bridging and chelating-bridging pseudo-oxo coordination modes while the 2,5-pzdc2- dianion exhibits a rather unusual bis-bidentate bridging pseudo-oxo coordination mode, both ligands being responsible for the stiffness of the resulting 3D structure. Solid-state photoluminescent measurements illustrate that 1 exhibits remarkable green luminescence emission, the most intense band occurring in the region of 550 nm (5D4 → 7F5) with lifetimes at the millisecond scale. Thermometric performances of 1 reveal a maximum relative sensitivity (Sm) of 0.76% K-1 at 295 K (δT = 0.05 K), constituting a TbIII ratiometric solid luminescent thermometer over the physiological temperature range. Variable-temperature static (dc) magnetic susceptibility measurements for 1 in the temperature range 2.0-300 K show the expected behavior for the depopulation of the splitted mJ levels of the 7F7 ground state of the magnetically anisotropic terbium(III) ion plus a weak antiferromagnetic interaction through the carboxylate bridges. No significant out-of-phase magnetic susceptibility signals were observed for 1 in the temperature range 2.0-10.0 K, either in the absence or presence of a static dc magnetic field.

Iso- and hetero-polyoxovanadium glycolates [VIV6O6(glyc)6MIII(OH)6]3- (M = V, Cr, Fe, and Al) encapsulating metal hydroxides.

Polyoxovanadium glycolates (NH4)3[V6O6(glyc)6V(μ-OH)6]·10H2O (1-V7) (H2glyc = glycolic acid) and its derivatives added with ammonium sulfates (NH4)3[V6O6(glyc)6M(μ-OH)6][(NH4)2SO4]2·xH2O (M = Cr, x = 6, 2-CrV6; M = Fe, x = 7, 3-FeV6; M = Al, x = 6, 4-AlV6) were obtained through self-assembly and fully characterized. Compounds 1-4 are composed of the same fully reduced cyclic {VIV6O6} unit bridged by six glycolate ligands. The framework encapsulated an octahedral metal(III) hydroxide {M(OH)6} (M = V3+, Cr3+, Fe3+, and Al3+) in the center, forming an iso- or hetero-heptanuclear Anderson-type structure. Moreover, two sulfate anions capped the two sides of cyclic {V6O6} units in compounds 2-4. Each sulfate formed a strong triple hydrogen bond (2.657-2.829 Å) with the μ3-OH group of the hydroxide. The sulfate anions played important roles in the formation of layered structures in 2-4, while the clusters were stacked compactly through strong hydrogen bonds in 1-V7. Because of the different central metals, these heptanuclear clusters exhibited distinct electronic structures as well as redox and magnetic properties. Magnetic studies showed that compounds 1-3 exhibited weak antiferromagnetic interactions in decreasing order with Fe3+, V3+ and Cr3+, while 4-AlV6 displayed weak ferromagnetic interactions. Their relationships with the local environment of the FeV-cofactor in V-nitrogenase are also discussed.

Crystal structure, optical, magnetic and antibacterial properties of a new tetrachlorocobaltate(II) salt with 4-nitrobenzyl substituted 2-methyl pyridinium

In this paper, a new organic-inorganic hybrid crystal material, 4-nitrobenzyl-2-methylpyridinium tetrachlorocobaltate(II) [4-NO2Bz-2-MePy]2[CoCl4](1), had been obtained by the slow-evaporation solution growth method. The single-crystal X-ray diffraction analysis showed that 1 crystallized in the monoclinic space group P21/n, composed of two [4-NO2Bz-2-MePy]+ cations and a [CoCl4]2− anion, where the cations represented Λ-shaped structure and the [CoCl4]2− anions exhibited a tetrahedral geometry. The PXRD spectrum confirmed the bulk phase purity, homogeneity, and crystalline nature of the material. The HOMO-LUMO energy gap and UV-visible diffuse reflectance spectrum explained the charge transfer interactions between the [CoCl4]2− anions and the [4-NO2Bz-2-MePy]+ cations. Furthermore, the low band gap values (1.27 eV for the experimental value and 1.65 eV for the calculated value) indicated the appropriateness of the crystal for optical applications. The first hyperpolarizability (βtot) of the salt was more than 6600 times higher than the standard KDP crystal (βKDP = 6.85 × 10−31 esu), suggesting that the title crystal was a superior material for NLO applications. The results of the antimicrobial experiment revealed that the compound exhibited excellent antimicrobial activity against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The title salt displayed weak antiferromagnetic interaction with the lowering of temperature.

Structural and Electronic Diversity as a Function of Metal Ions and Co‐ligands in Deprotonated Epindolidione Bridged Diruthenium and Diosmium Set‐up

AbstractThe article dealt with the structurally validated L2− (H2L=epindolidione=5,11‐dihydroquinolino[3,2‐b]quinoline‐6,12‐dione, a heteroatom‐modified tetracene and a structural isomer of indigo dye) bridged {(acac)2RuIII}2(μ‐L2−) 1/2 (S=1, acac=acetylacetonate) and [{(bpy)2OsII}2(μ‐L2−)](ClO4)2 [3](ClO4)2/[(pap)2OsII}2(μ‐L2−)](ClO4)2 [4](ClO4)2 (S=0, bpy=2,2′‐bipyridine, pap=2‐phenylazopyridine). 1/2 and [3](ClO4)2/[4](ClO4)2 with a metal‐metal separation of ≈7 Å stabilized selectively in meso(ΔΛ)/rac(ΔΔ/ΛΛ) and meso diastereomeric forms, respectively, in spite of calculated minor difference in energy between the diastereomers in each case. Though 2, [3](ClO4)2/[4](ClO4)2) exhibited intermolecular π–π interactions, no such non‐covalent interaction was perceived in 1. RuIIIRuIII derived 1/2 (S=1, 2.63/2.57 μB at 300 K) attributed to non‐interacting two Ru(III) (S=1/2) spins with an intermolecular through space weak antiferromagnetic exchange interaction below 12 K and its variable temperature 1H NMR revealed Fermi and pseudo‐contact shifts. Multiple redox steps of the complexes varied as a function of metal ion (Ru versus Os), its oxidation state (III versus II) and ancillary ligand (acac versus bpy versus pap). A collective consideration of DFT calculated MOs and Mulliken spin densities suggested delicate electronic forms along the redox chain due to the participation of bridge largely in the oxidation processes as a consequence of its redox non‐innocent feature. Reductions were however mostly centered around the metal (RuIII to RuII) and ancillary ligands (bpy/pap) in 1/2 and 32+/42+, respectively. 1n/2n, [3]2+/[4]2+ displayed mixed metal/ligand based weak low‐energy (800‐1400 nm) transitions in addition to intense visible bands as corroborated by TD‐DFT calculations.