Types Of Bridging Ligands Research Articles

Antiviral, Antibacterial, Antifungal, and Cytotoxic Silver(I) BioMOF Assembled from 1,3,5-Triaza-7-Phoshaadamantane and Pyromellitic Acid.

The present study reports the synthesis, characterization, and crystal structure of a novel bioactive metal-organic framework, [Ag4(µ-PTA)2(µ3-PTA)2(µ4-pma)(H2O)2]n·6nH2O (bioMOF 1), which was assembled from silver(I) oxide, 1,3,5-triaza-7-phosphaadamantane (PTA), and pyromellitic acid (H4pma). This product was isolated as a stable microcrystalline solid and characterized by standard methods, including elemental analysis, 1H and 31P{1H} NMR and FTIR spectroscopy, and single crystal X-ray diffraction. The crystal structure of 1 disclosed a very complex ribbon-pillared 3D metal-organic framework driven by three different types of bridging ligands (µ-PTA, µ3-PTA, and µ4-pma4−). Various bioactivity characteristics of bioMOF 1 were investigated, revealing that this compound acts as a potent antimicrobial against pathogenic strains of standard Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria, as well as a yeast (Candida albicans). Further, 1 showed significant antiviral activity against human adenovirus 36 (HAdV-36). Finally, bioMOF 1 revealed high cytotoxicity toward an abnormal epithelioid cervix carcinoma (HeLa) cell line with low toxicity toward a normal human dermal fibroblast (NHDF) cell line. This study not only broadens the family of PTA-based coordination polymers but also highlights their promising multifaceted bioactivity.

Synthesis, Structural and Physicochemical Properties of Water-Soluble Mixed-Ligand Diruthenium Complexes Containing Anilinopyridinate Bridging Ligands.

A series of water-soluble Ru25+ complexes of the type Ru2(O2CCH3)3(L)Cl where L = 2,3,4,5,6-F5ap, 2,4,6-F3ap, 2-Fap, ap, 2-Meap, 2,6-Me2ap, or 2,4,6-Me3ap, where ap is the anilinopyridinate anion, have been characterized as to their structural and physicochemical properties in H2O and DMSO. Five of the newly synthesized complexes were structurally characterized, and the Ru-Cl bond lengths range from 2.477 to 2.544 Å while the Ru-Ru bond lengths range from 2.2838 to 2.2935 Å. The UV-vis spectra of each compound are characterized by three absorption bands in both H2O and DMSO, the intensity and position of which vary with both the type of bridging ligand and the solvent. The seven examined Ru25+ complexes exist as 1:1 electrolytes in water, and each undergoes a reversible one-electron reduction assigned to Ru25+/Ru24+ in both investigated solvents. A second irreversible reduction attributed to Ru24+/Ru23+ is also observed for each compound at more negative potentials in DMSO. A linear free energy relationship exists between the sum of the Hammett substituent constants (Σσ) on the ap-type bridging ligand and the wavenumber of an absorption band for the Ru25+ complexes. A linear relationship is also seen between Σσ and measured E1/2 values for the Ru25+/Ru24+ process in water containing 0.1 M KCl, but little to no effect is seen between the specific bridging ligand and the structural features of the investigated compounds.

Three different types of bridging ligands in a 3d-3d'-3d'' heterotrimetallic chain.

A one-pot synthesis of a 3d-3d'-3d'' heterotrimetallic coordination polymer with double diphenoxido, single cyanido and bis-bidentate oxalate as alternating bridges which exhibits an overall antiferromagnetic behaviour has been developed.

Dimension and bridging ligand effects on Mo-mediated catalytic transformation of dinitrogen to ammonia: Chain-like extended models of Nishibayashi’s catalyst

Previous studies suggested that in Nishibayashi’s homogenous catalytic systems based on molybdenum (Mo) complexes, the bimetallic structure facilitated dinitrogen to ammonia conversion in comparison to the corresponding monometallic complexes, likely due to the through-bond interactions between the two Mo centers. However, more detailed model systems are necessary to support this bimetallic hypothesis, and to elucidate the multi-metallic effects on the catalytic mechanism. In this work, we computationally examined the effects of dimension as well as the types of bridging ligands on the catalytic activities of molybdenum-dinitrogen complexes by using a set of extended model systems based on Nishibayashi’s bimetallic structure. The polynuclear chains containing four ([Mo]4) or more Mo centers were found to drastically enhance the catalytic performance by comparing with both the monometallic and bimetallic complexes. Carbide ([:CC:]2−) was found to be a more effective bridging ligand than N2 in terms of electronic charges dispersion between metal centers thereby facilitating reactions in the catalytic cycle. The mechanistic modelling suggests that in principle, more efficient catalytic system for N2 to NH3 transformation might be obtained by extending the polynuclear chain to a proper size in combination with an effective bridging ligand for charge dispersion.

A Benzaldehyde Derivative as a Chelating Ligand: Helical Manganese(II) Coordination Polymers Assembling into a Porous Solid

A molecular, porous crystalline material constructed from neutral helical coordination polymers incorporating manganese(II) ions and two types of bridging ligands, namely the deprotonated form of 2-hydroxy-5-methoxy-3-nitrobenzaldehyde (HL) and isobutyrate (iB–), has been obtained and structurally characterized. Structural analysis reveals that within the coordination polymer each benzaldehyde derivative ligates two manganese ions in 6-membered chelating rings, and the isobutyrate ligands cooperatively chelate either two or three manganese ions. The solid state assembly of the resulting polymeric chains of formula [Mn4(L)2(iB)6]n (1), described in the polar space group R3c, is associated with tubular channels occupied by MeCN solvent molecules (1·xMeCN; x ≤ 9). TGA profiles and PXRD measurements demonstrate that the crystallinity of the solid remains intact in its fully desolvated form, and its stability and crystallinity are ensured up to a temperature of 190 °C. Gas adsorption properties of desolvated crystals were probed, but no remarkable sorption capacity of N2 and only a limited one for CO2 could be observed. Magnetic susceptibility data reveal an antiferromagnetic type of coupling between adjacent manganese(II) ions along the helical chains with energy parameters J1 = −5.9(6) cm–1 and J2 = −1.8(9) cm–1.

Synthesis and structure of coordination polymers of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ by combination of bipyrazole and diphenate ligands

Five new coordination polymers, [Mn(DPA)(Me4bpz)(H2O)](I)∞1, [Cu(DPA)(Me4bpz)2]·H2O(II)∞1, [Ag4(OAc)2(Me4bpz)3(H2O)1.56](III)∞2, [Zn(DPA)(Me4bpz)]·0.61H2O(IV)∞3 and [Cd(DPA)(Me4bpz)](V)∞3[DPA: diphenic acid dianion, OAc: acetate, Me4bpz: 3,3′,5,5′-tetramethyl-4,4′-bipyrazole], were obtained from acetate hydrates of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ and a mixed ligand system consisting of Me4bpz and diphenic acid by hydrothermal synthesis under similar conditions. Their crystal structures were determined by means of X-ray single crystal structure analysis. Furthermore, the compounds were characterized by means of elemental analysis and IR spectroscopy. The polymers I and II exhibit one-dimensional chain structures with only one type of bridging ligand, whereas the polymers IV and V realize three-dimensional coordination frameworks with diamond topology involving both ligand types as bridging ligands. Compound III contains a two-dimensional cationic framework which is charge compensated by acetate anions. The coordination environments of the metal centers are predominant directly supported by N–H⋯O hydrogen bonds providing further evidence for the bipyrazole-carboxylate supramolecular synthon.

Hybrid-DFT Study on Electronic Structures of the Active Site of Sweet Potato Purple Acid Phosphatase: The Origin of Stronger Antiferromagnetic Couplings than Other Purple Acid Phosphatases

The electronic structure and magnetic interactions of the active site of sweet potato purple acid phosphatase (PAP) were investigated by using UHF, pure DFT (UBLYP), and hybrid DFT methods (UB3LYP and UB2LYP). PAP catalyzes the hydrolysis of a phosphate ester under acidic conditions and contains a binuclear metal center. Sweet potato PAP provides stronger antiferromagnetic coupling than other PAPs. UB3LYP showed reasonably good agreement with the experimental magnetic coupling, indicating that this stronger antiferromagnetic coupling is caused by a mu-oxo bridge in the Fe(III)-Mn(II) binuclear metal center, which is the origin of the asymmetric spin delocalization. The type of bridging ligand is essential for the reaction mechanism, because the bridging ligand is suggested to function as a nucleophile in the reaction. Analyses of the natural orbital and spin density distributions implied the asymmetric spin delocalization on the bridging oxygen. The mechanism and the pathway of the antiferromagnetic coupling between Fe(III) and Mn(II) were discussed, using chemical indices introduced with the occupation numbers of singly occupied natural orbitals.

Self-assembly of mixed-valence Co(ii/iii) and Ni(ii) clusters: azide-bridged 1D single chain coordination polymers comprised of tetranuclear units, tetranuclear Co(ii/iii) complexes, ferromagnetically coupled azide-bridged tetranuclear, and hexanuclear Ni(ii) complexes: synthesis, structural, and magnetic properties

One-pot reactions between 2,6-diformyl-4-methylphenol (DFMP) and 2-aminoethanol (AE) in the presence of cobalt(II) salts [Co(ClO4)2, CoCl2, Co(CH3CO2)2, Co(NO3)2] and sodium azide result in the self-assembly of novel one-dimensional single chain mixed-valence cobalt coordination polymers {[Co2(II)Co2(III) (HL)2(OCH3)2(N3)3]ClO(4).5H2O.CH3OH}n (1), {[Co2(II)Co2(III) (HL)2(OCH3)2(N3)3]Cl.H2O}n (2) in which tetra-cobalt cationic units are bridged by symmetrical 1,3-azides, forming single chains; mixed valence neutral tetranuclear clusters [Co2(II)Co2(III) (HL)2(OCH3)2(N3)4]CH3OH.2H2O (3), [Co2(II)Co2(III)(HL)2(OCH3)2(N3)2(CH3CO2)2].2CH3OH.2H2O (4), and the cationic cluster [Co2(II) Co2(III) (HL)2(OCH3)2(CH3OH)2(N3)2](NO3)2 (5). In all these reactions, H3L, the potentially pentadentate (N2O3), trianionic double Schiff base ligand 2,6-bis[(2-hydroxy-ethylimino)-methyl]-4-methylphenol is formed. The reaction between DFMP and AE in the presence of nickel(ii) salts and sodium azide in methanol-water mixture results in the self-assembly of ferromagnetically coupled hexanuclear complexes [Ni6(H2L)2(HL-1)2(H2O)2(N3)6](ClO4)(2).2CH3OH (6), and [Ni6(H2L)2(HL-1)2(CH3OH)2(N3)6](BF4)2 (7), involving double (H3L) and single (H2L-1) Schiff base ligands, and a neutral tetranuclear complex [Ni4(H2L)2(OCH3)2(CH3CO2)2(N3)2] (8) with only double Schiff-base (H3L). In these complexes, the nature of the anion and the reaction conditions seem to play an important role in directing the formation of tetranuclear, hexanuclear or polymeric clusters. All complexes involve divacant double cubane-type cores containing three to four different types of bridging ligands (phenoxy, azido, methoxy/alkoxy, and acetate). Variable temperature magnetic properties of these spin coupled clusters have been investigated and magneto-structural correlations have been established.

Recent Advances in the Design and Construction of Helical Coordination Polymers

AbstractFor Abstract see ChemInform Abstract in Full Text.

Theoretical study of the magnetic behavior of [Fe8] and [Fe16] wheels.

The reaction of the trimetallic species [Fe(3)O(PhCOO)(6)(H(2)O)(3)]NO(3) with 1,1,1-tris(hydroxymethyl)ethane (H(3)thme) affords either the octametallic species [Fe(8)(PhCOO)(12)(thme)(4)] 1 or the hexadecametallic species [Fe(16)(EtO)(4)(PhCOO)(16)(Hthme)(12)](NO(3))(4) 2, depending on the nature of the solvent used for crystallization. The structure of 1 can be described as a nonplanar wheel of eight Fe(III) ions bridged by a combination of PhCOO(-) and thme(3)(-) ligands, and 2 as a nonplanar wheel of sixteen Fe(III) ions bridged by PhCOO(-), Hthme(2)(-), and EtO(-) ligands. Both compounds can be broken down into simple units of two metal ions and the bridging ligands that connect them. The best fits of the chi vs T curves in the 300-10 K temperature range were obtained with the parameters g = 2.0, J(1) = -24.0 cm(-1), and J(2) = -8.59 cm(-1) for [Fe(8)] and g = 2.0, J(1) = -25.0 cm(-1), J(2) = -11.73 cm(-1), and J(3) = -69.3 cm(-1) for [Fe(16)]. Density functional theory (DFT) calculations show that the antiferromagnetic interactions between the metals in the dinuclear units decrease when two types of bridging ligands are present, as expected for an orbital counter-complementarity effect.

Syntheses and crystal structures of iron co-ordination polymers with 4,4′-bipyridine (4,4′-bpy) and 4,4′-azopyridine (azpy). Two-dimensional networks supported by hydrogen bonding, {[Fe(azpy)(NCS)2(MeOH)2]·azpy}n and {[Fe(4,4′-bpy)(NCS)2(H2O)2]·4,4′-bpy}n

New iron(II) co-ordination polymers, {[Fe(azpy)(NCS)2(MeOH)2]·azpy}n 1 (azpy = 4,4′-azopyridine), {[Fe(4,4′-bpy)(NCS)2(H2O)2]·4,4′-bpy}n 2 (4,4′-bpy = 4,4′-bipyridine) and {[Fe(azpy)2(NCS)2]·3H2O}n 3 have been synthesized and characterized. The crystal structures of both compounds 1 and 2 contain two types of bridging ligands; one is of the co-ordination bond type, directly bridging iron centers to form a one-dimensional chain of [Fe(L)] (L = azpy or 4,4′-bpy), while the other links these chains by hydrogen bonds between the pyridine nitrogen atoms and co-ordinated methanol or water molecules, resulting in a grid sheet. Each sheet shows non-interpenetration because of incorporation of NCS anion in the grid. Cyclic voltammograms of 1 and 3 demonstrate that the directly bridging azpy ligands show no apparent redox activity, whereas a reversible redox wave observed for 1 is attributed to the hydrogen-bonding supported azpy. Magnetic susceptibilities measured from 1.9 to 300 K are indicative of no appreciable magnetic exchange interaction between the adjacent metal ions.

“Platinum blue” complex with a new type of bridging ligand

A new paramagnetic tetrameric “Platinum Blue” complex with the bioligand creatin was synthetized and its structure studied by means of IR and EPR spectroscopy. It is shown that the guanidine part of the ligand molecule, namely HN = CNH 2, is serving as a bridge between the “Platinum Blues” similarly to amide and α-diacetyl groups.

Directional energy transfer in a luminescent tetranuclear Ru(II) polypyridine complex that contains two different types of bridging ligands

Directional energy transfer in a luminescent tetranuclear Ru(II) polypyridine complex that contains two different types of bridging ligands