OH Anions Research Articles

On the complex structural diffusion of proton holes in nanoconfined alkaline solutions within slit pores.

The hydroxide anion OH−(aq) in homogeneous bulk water, that is, the solvated proton hole, is known to feature peculiar properties compared with excess protons solvated therein. In this work, it is disclosed that nanoconfinement of such alkaline aqueous solutions strongly affects the key structural and dynamical properties of OH−(aq) compared with the bulk limit. The combined effect of the preferred hypercoordinated solvation pattern of OH−(aq), its preferred perpendicular orientation relative to the confining surfaces, the pronounced layering of nanoconfined water and the topology of the hydrogen bond network required for proton hole transfer lead to major changes of the charge transport mechanism, in such a way that the proton hole migration mechanism depends exquisitely on the width of the confined space that hosts the water film. Moreover, the anionic Zundel complex, which is of transient nature in homogeneous bulk solutions, can be dynamically trapped as a shallow intermediate species by suitable nanoconfinement conditions.

Solid solution in the apatite OH-Cl binary system: Compositional dependence of solid-solution mechanisms in calcium phosphate apatites along the Cl-OH binary

The method of accommodation of solid solution along the OH-Cl binary in calcium phosphate apatites is not fully understood; because of steric constraints in mixtures of OH and Cl anions in the apatite [0,0, z ] anion column, the positions of OH and Cl anions in the pure hydroxylapatite and chlorapatite end-members cannot coexist in the binary anion column. We have undertaken high-precision single-crystal X-ray structure studies of eight synthetic samples along the OH-Cl apatite binary ( R 1 ≈ 0.0159). We found that for all samples solid solution is attainable in space group P 6 3 / m , but the particular method of solid solution depends on composition. For samples with Cl > OH, three column anion sites (two for Cl, one for OH) provide allowable bond distances with the Ca2 atoms and allow a sequence of column anions that provides sufficient anion-anion distances and also effects reversal of the sense of ordering of the column anions relative to the mirror planes at z = ¼ and ¾. In a sample with OH > Cl, three sites exist in the anion column that also provide allowable bond distances to the triangle of Ca2 atoms or its disordered Ca2′ equivalent, and afford a sequence of atoms that permits reversal of the anion column and maintenance of P 6 3 / m symmetry. One of those sites is occupied by OH and provides acceptable Ca2-OH distances, and another accommodates Cl with ideal Ca2-Cl distances. A third column anion site is unique among the calcium phosphate apatites. That site, termed the ClOH site, accommodates both OH and Cl. The site has an ideal bond distance for OH to the Ca2 atoms in the Ca2 triangle and also has an ideal bond distance for a Cl occupant to disordered Ca2′ atoms; thus, because of the disordering of the Ca2-Ca2′ atoms, a single site can accommodate either anion with ideal, but disparate, bond distances to Ca. Finally, in OH-Cl apatites with OH ≈ Cl, also crystallizing in space group P 6 3 / m , four anion positions are occupied in the anion column, including the ClOH site that allows occupancy by both OH and Cl. In addition to that site and distinct OH and Cl sites, OH is found to occupy the site within the mirror plane at (0,0,¼), the site occupied by F in F-bearing apatite. Occupancy of that site is essential to reversing the sense of ordering of the anion column relative to the mirror planes and preserving P 6 3 / m symmetry. Thus, the methods of effecting solid solution along the OH-Cl are composition dependent and complex.

Sonocatalytic degradation of diclofenac with FeCeOx particles in water

This paper studies the sonocatalytic degradation of diclofenac in water using FeCeOx-catalyzed ultrasound. The effects of pre-adsorption and gas addition were investigated. Nitrogen adsorption/desorption, SEM, XRD, Raman and XPS analyses of FeCeOx before and after sonication were characterized. The proposed mechanism was based on the microstructure changes of FeCeOx and reactive-species-scavenging performances. The results show that FeCeOx has excellent performance in catalyzing an ultrasonic system in water, and 80% of diclofenac was removed in 30min ([Diclofenac]=20mg/L, FeCeOx amount=0.5g/L, pH=6, ultrasonic density=3.0W/cm3, ultrasonic frequency=20kHz, temperature=298K). The Fe, Ce, and O elements remained highly dispersed in the structure of FeCeOx, and the solid solution structure of FeCeOx remained stable after the reaction. Ce (III) was gradually oxidized to Ce (IV) and Fe (III) was gradually reduced to Fe (II) after the reaction, which indicates that Fe and Ce ions with different valences coexisted in dynamic equilibrium. The amount of oxygen vacancies in FeCeOx significantly decreased after the reaction, which indicates that oxygen vacancy participated in the ultrasonic process. Singlet oxygen 1O2 was the primary reactive species in the degradation process, and the hydroxyl radicals OH and superoxide radical anion O2− also participated in the reaction. FeCeOx had excellent chemical stability with negligible leaching ions in the ultrasonic process.

The non-IRC mechanism of OH anion reaction with CH3OOH revealed by direct dynamics simulations

Organic peroxides are temporary reservoirs for oxidizing radicals and are involved in the formation of acid rain, so it is important to remove them in the atmosphere. The elimination reaction of CH3OOH with hydroxide anion has been investigated by direct dynamics simulations at PBE0/6-311+G(d,p) level of theory. Two products channels, CH3OO−+H2O and H2O+CH2O+HO−, are observed. 44% formed CH3OO−+H2O, the major product reaction channel observed in experiment, 27% formed HO−+CH2O+H2O and remaining 29% trajectories went back to the reactants. The simulations reveal that two reaction channels occur by both direct and indirect events and dominate by the direct mechanism. The non-IRC behavior is found for this reaction, that the much higher energy non-IRC products CH3OO−+H2O and H2O+CH2O+HO− were formed, instead of the more exothermic products H2O+CH2(OH)O− as predicted by the intrinsic reaction coordinate (IRC).

The potential energy surface of OH anion reaction with CH3OOH: Theoretical investigations

Removing ROOH in the atmosphere is important because they can lead to the redistribution of HOx and ROx radicals, which regulate the oxidation capacity of the atmosphere. The MP2 method and the B3LYP and PBE0 DFT functionals, with 6-31++G∗∗ and aug-cc-pVDZ basis sets were employed to determine the geometries, reaction paths and mechanisms of OH−+CH3OOH reaction. Single point energy calculations were carried out at CCSD(T)/aug-cc-pVDZ level of theory served as benchmark. Although B3LYP energies gives the best agreement to the benchmark, it failed to locate TS1. PBE0/6-311+G(d,p) is chosen as an appropriate method for the dynamics simulations. Four product channels are observed, where CH3OO−+H2O and H2O+CH2O+HO− are competitive due to the similar barrier height, and H2O+CH2(OH)O− is the most exothermic product, and in contrast, CH3OH+HOO− is the least feasible one. The PES results are not consistent with the experimental observation where product H2O+CH2(OH)O− is not found, which might attribute to a “rough” landscape of PES after passing a rate controlling transition state, implying a non-IRC behavior for this reaction.

Comparative study on the increased photoactivity of coupled and supported manganese-silver oxides onto a natural zeolite nano-particles

Supported MnO, Ag2O and MnO-Ag2O onto clinoptilolite nano-particles (NCP) were used for the photodecolorization of methylene blue (MB) aqueous solution. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflection spectroscopy (DRS), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) and Fourier transformation infra-red (FTIR). DRS results showed red shifts in band gap energies of the supported MnO-Ag2O semiconductors with respect to the supported monocomponent one (MnO or Ag2O). Also, in the coupled semiconductors Ag2O-conduction band (CB) potential (E°=−1.3V) is enough negative to immigrate the photogenerated electrons from this level to MnO-CB level (E°=0.1V). This significantly prevent from electron/hole recombination which caused to increase the photocatalytic activity. Due to more negative potential of Ag2O-CB level than oxygen potential reduction, the photogenerated electrons in Ag2O-CB can change oxygen molecules to superoxide radical and hydrogen peroxide. The produced H2O2 molecules can break to hydroxyl radicals during the irradiation process. In contrast, valence band (VB) potential of MnO (E°=2.4V) is sufficient for oxidation of water molecules or OH anions to hydroxyl radicals. Adding sodium chloride and potassium bromated to the system caused to decrease the photocatalytic activity because these OH scavengers produce other radicals such as OCl (E°=1.5V), HOBr (E°=2.4V) and BrO2 (E°=1.2V) which have less oxidizing power the powerful OH (E°=2.8V). Photocatalytic results showed that the hybridized MnO-Ag2O/NCP catalyst containing 10% MnO and 2.1% Ag2O was more effective than the non-hybridized MnO/NCP and Ag2O/NCP. The declororization process obeyed the first-order kinetics. Some photodecloriztion intermediates such as phenol and aniline were recognized by GC-Mass.

Performance Enhancement and Side Reactions in Rechargeable Nickel–Iron Batteries with Nanostructured Electrodes

We report for the first time a solution-based synthesis of strongly coupled nanoFe/multiwalled carbon nanotube (MWCNT) and nanoNiO/MWCNT nanocomposite materials for use as anodes and cathodes in rechargeable alkaline Ni-Fe batteries. The produced aqueous batteries demonstrate very high discharge capacities (800 mAh gFe(-1) at 200 mA g(-1) current density), which exceed that of commercial Ni-Fe cells by nearly 1 order of magnitude at comparable current densities. These cells also showed the lack of any "activation", typical in commercial batteries, where low initial capacity slowly increases during the initial 20-50 cycles. The use of a highly conductive MWCNT network allows for high-capacity utilization because of rapid and efficient electron transport to active metal nanoparticles in oxidized [such as Fe(OH)2 or Fe3O4] states. The flexible nature of MWCNTs accommodates significant volume changes taking place during phase transformation accompanying reduction-oxidation reactions in metal electrodes. At the same time, we report and discuss that high surface areas of active nanoparticles lead to multiple side reactions. Dissolution of Fe anodes leads to reprecipitation of significantly larger anode particles. Dissolution of Ni cathodes leads to precipitation of Ni metal on the anode, thus blocking transport of OH(-) anions. The electrolyte molarity and composition have a significant impact on the capacity utilization and cycling stability.

Collisional state-changing of OH− rotations by interaction with Rb atoms in cold traps

We employ an accurate, ab initio potential energy surface (PES) which describes the electronic interaction energy between the molecular anion OH− (1Σ+) and the neutral rubidium atom Rb (2S), to evaluate the elastic and inelastic cross sections over a range of energies representative of the conditions of low-T experiments in MOT traps, when combined with laser-cooled rubidium gas. The system is considered to be in its vibrational ground state, while the first four rotational levels are taken to be involved in the cooling and heating collisional processes that are computed here.The corresponding cooling and heating rates up to about 35K are obtained from the calculations and compared with the recent results in a similar experiments, where He was the partner atom of the current anion.

Two-photon rotational action spectroscopy of cold OH- at 1 ppb accuracy.

The fundamental rotational transition J = 1←0 of the anion OH(-) has been measured by cooling mass-selected OH(-) ions to 10 K in a 22-pole ion trap and applying a novel rotational-rovibrational two-photon scheme. A transition frequency of (1 123 101.0410 ± 0.0014) MHz was obtained with so far unprecedented accuracy. The general application of the presented action-spectroscopy scheme to other anions and cations is discussed.

Tracking plasma generated H2O2 from gas into liquid phase and revealing its dominant impact on human skin cells

The pathway of the biologically active molecule hydrogen peroxide (H2O2) from the plasma generation in the gas phase by an atmospheric pressure argon plasma jet, to its transition into the liquid phase and finally to its inhibiting effect on human skin cells is investigated for different feed gas humidity settings. Gas phase diagnostics like Fourier transformed infrared spectroscopy and laser induced fluorescence spectroscopy on hydroxyl radicals (·OH) are combined with liquid analytics such as chemical assays and electron paramagnetic resonance spectroscopy. Furthermore, the viability of human skin cells is measured by Alamar Blue® assay. By comparing the gas phase results with chemical simulations in the far field, H2O2 generation and destruction processes are clearly identified. The net production rate of H2O2 in the gas phase is almost identical to the H2O2 net production rate in the liquid phase. Moreover, by mimicking the H2O2 generation of the plasma jet with the help of an H2O2 bubbler it is concluded that the solubility of gas phase H2O2 plays a major role in generating hydrogen peroxide in the liquid. Furthermore, it is shown that H2O2 concentration correlates remarkably well with the cell viability. Other species in the liquid like ·OH or superoxide anion radical do not vary significantly with feed gas humidity.

Anion stripping as a general method to create cationic porous framework with mobile anions.

Metal-organic frameworks (MOFs) with cationic frameworks and mobile anions have many applications from sensing, anion exchange and separation, to fast ion conductivity. Despite recent progress, the vast majority of MOFs have neutral frameworks. A common mechanism for the formation of neutral frameworks is the attachment of anionic species such as F(-) or OH(-) to the framework metal sites, neutralizing an otherwise cationic scaffolding. Here, we report a general method capable of converting such neutral frameworks directly into cationic ones with concurrent generation of mobile anions. Our method is based on the differential affinity between distinct metal ions with framework anionic species. Specifically, Al(3+) is used to strip F(-) anions away from framework Cr(3+) sites, leading to cationic frameworks with mobile Cl(-) anions. The subsequent anion exchange with OH(-) further leads to a porous network with mobile OH(-) anions. New materials prepared by anion stripping can undergo ion exchange with anionic organic dyes and also exhibit much improved ionic conductivity compared to the original unmodified MOFs.

Sr4B10O18(OH)2·2H2O: a new UV nonlinear optical material with a [B10O23]16−building block

A new ultraviolet (UV) nonlinear optical (NLO) crystal Sr4B10O18(OH)2·2H2O has been synthesized using the hydrothermal method. It crystallizes in the triclinic space group P1 (no. 1) with lattice constants a = 6.4991(6) A, b = 6.5059(6) A, c = 11.3175(11) A, α = 88.458(6)°, β = 86.019(5)°, γ = 61.351(5)°, Z = 1. The fundamental building block of the structure is a [B10O23]16− unit which consists of two stereo-isomeric configurations of [B5O12]9− groups. The structure exhibits a ∞[B10O18]6− three dimensional network with 9-membered tunnels along the b-axis where the Sr cation, OH anion and H2O molecule are located. Powder second harmonic generation (SHG) measurements indicate that Sr4B10O18(OH)2·2H2O is type-I phase-matchable and displays a SHG response of about 2 × KH2PO4. The UV-Vis-NIR diffuse reflectance spectrum shows that its cutoff edge is lower than 190 nm. Density functional theory (DFT) calculations on electronic structures and SHG coefficients confirm the experimental results.

Theoretical simulation of reduction mechanism of graphene oxide in sodium hydroxide solution.

Based on a density functional theory simulation, we proposed a reduction mechanism of graphene oxide (GO) under a sodium hydroxide solution containing anions (OH(-)), cations (Na(+)) and neutral H2O molecules as main components. OH(-) anion can interact with hydroxyl in GO and transfer electrons to the graphene sheet, resulting in negatively charged GO, and these electrons obviously lower the barrier of the ring-opening reaction of epoxy. Na(+) cations can be attracted by the negatively charged GO, and this reaction is equivalent to the one between metallic Na and GO. The opened epoxy is reduced with the assistance of Na(+) cation and water molecule. In such a reduction process, NaOH can be viewed as a catalyst and more defects should be formed because of these diffused epoxies on the negatively charged graphene sheet. Our results may be helpful to understand further the nature of the reduction of GO among various reducing agents.

Nature of Zr-Monosubstituted Monomeric and Dimeric Polyoxometalates in Water Solution at Different pH Conditions: Static Density Functional Theory Calculations and Dynamic Simulations

Static density functional theory (DFT) calculations with a continuous solvent model as well as classical and Car-Parrinello molecular dynamics (MD) simulations with explicit solvent molecules were performed to study the nature of Zr-monosubstituted monomeric and dimeric polyoxometalates (POMs) in water at different pHs. We have analyzed Zr-aqua, -hydroxo, and -aqua-hydroxo species derived from Linqvist- and Keggin-type anions. Both DFT and Car-Parrinello MD methods suggest that the Zr center tends to have coordination number greater than 6 and can bind up to 3 water molecules. Car-Parrinello MD simulations also show that the Zr atom fluctuates within the oxide POM framework, providing a flexible coordination environment. There is a small thermodynamic preference for the Zr-aqua species over the protonated Zr-hydroxo species; however the prevalence of one or the other species might depend on the pH. Classical MD simulations show that H3O(+) interacts mainly with hydroxo ligand, while OH(-) anions prefer the protons of the H2O ligands. In general, an increase of the acidity favors the formation of Zr-aqua species, explaining why dimer dissociation is promoted at low pH. At basic conditions Zr-hydroxo species are generated, providing the reactive groups to form Zr···Zr linkages.

Stabilization of the Triphosphallyl Ligand η3‐P3{P(O)H} at Iridium via Alkaline Activation of P4

The selective functionalization of the polyphosphorus moiety Ph2PCH2PPh2PPPP present as a tetrahapto-ligand in complex [Ir(dppm)(Ph2PCH2PPh2PPPP)](+) (1, dppm=Ph2PCH2PPh2) was obtained by reaction of 1 with water under basic conditions at room temperature. The formation of the new triphosphaallyl moiety η(3)-P3{P(O)H} was determined in solution by NMR spectroscopy, and confirmed in the solid state by a single-crystal X-ray structure of the stable product [Ir(κ(2)-dppm)(κ(1)-dppm)(η(3)-P3{P(O)H})] (2). In solution, 2 has a fluxional behavior attributable to the four P atoms belonging to the tetraphosphorus moiety in 1 and exhibits a chemical exchange process involving the two PPh2 moieties of the same bidentate ligand, as determined by 1D and 2D NMR spectroscopy experiments carried out at variable temperature. The mechanism of the reaction was investigated at the DFT level, which suggested a selective attack of an in-situ generated OH(-) anion on one of the non-coordinated phosphorus atoms of the P4 moiety. The reaction then evolves through an acid-assisted tautomerization, which leads to the final compound 2. Bonding analysis pointed out that the new unsubstituted P3-unit in the η(3)-P3{P(O)H} moiety behaves as a triphosphallyl ligand.

Sodium-Centered Dodecanuclear Co(II) and Ni(II) Complexes with 2-(Phosphonomethylamino)succinic Acid: Studies of Spectroscopic, Structural, and Magnetic Properties

Two new isostructural cobalt(II) and nickel(II) polynuclear complexes with 2-(phosphonomethyl)aminosuccinic acid, H4PMAS, namely, Na[Co12(PMAS)6(H2O)17(OH)]·x2H2O, 1·x2H2O, and Na[Ni12(PMAS)6(H2O)17(OH)]·xH2O, 2·xH2O, have been synthesized for the first time from aqueous solutions and studied by single crystal X-ray diffraction, infrared, and UV-visible diffuse reflectance spectroscopy; TG/DTA analysis; and magnetochemistry. Both 1 and 2 crystallize in the rhombohedral crystal system with the R3[overline] space group with 1/6 of the Co12(PMAS)6 or Ni12(PMAS)6 moieties in the asymmetric unit. The X-ray refinements reveal the presence of 18 water sites, but unit cell charge balance requires that one water molecule must be an OH(-) anion, an anion which is disordered over the 18 sites. The PMAS(4-) ligand forms two five-membered and one six-membered chelation ring. Both 1 and 2 contain 24-membered metallacycles as a result of the bridging nature of the PMAS(4-) ligands. The resulting three-dimensional structures have one-dimensional channels with a sodium cation at the center of symmetry. The temperature dependence of the magnetic susceptibility reveals the presence of weak antiferromagnetic exchange coupling interactions in both 1 and 2. Two exchange coupling constants, J1 = -15.3(7) cm(-1) and J2 = -1.06(2) cm(-1) with S1 = S2 = 3/2 for the Co(1)···Co(1) and Co(1)···Co(2) exchange pathways, respectively, are required for 1, and J1 = -1.17(6) cm(-1) and J2 = -4.00(8) cm(-1) with S1 = S2 = 1 for the Ni(1)···Ni(1) and Ni(1)···Ni(2) exchange pathways, respectively, are required for 2, in order to fit the temperature dependence of the observed magnetic susceptibilities.

Morphology‐photocatalytic properties‐growth mechanism for ZnO nanostructures via microwave‐assisted hydrothermal synthesis

AbstractZnO nanostructures with various morphologies including rod‐like, sheet‐like, needle‐like and flower‐like structures were successfully synthesized via a fast and facile microwave‐assisted hydrothermal process. Reaction temperature, reaction time and the addition of NaOH were adjusted to obtain ZnO with different morphologies. Scanning electron microscopy(SEM), transmission electron microscope(TEM), X‐ray diffraction (XRD) and ultraviolet spectrophotometer (UV) were used to observe the morphology, crystal structure, ultraviolet absorption and photocatalytic activity of the obtained ZnO. The results indicated that growth rate of ZnO nanostructure along [001] direction was more sensitive to temperature compared with those along [101] and [100] directions. The competition between anionic surfactant and OH− played an important role in the formation of ZnO with various morphologies. Flower‐like ZnO had better ultraviolet absorption property and excellent photocatalytic activity than ZnO in the other morphologies. On the basis of the above results, a possible growth mechanism for the formation of ZnO nanostructures with different morphologies was described.

Different Nature of the Interactions between Anions and HAT(CN)6: From Reversible Anion−π Complexes to Irreversible Electron-Transfer Processes (HAT(CN)6 = 1,4,5,8,9,12-Hexaazatriphenylene)

We report experimental evidence indicating that the nature of the interaction established between HAT(CN)(6), a well-known strong electron acceptor aromatic compound, with mono- or polyatomic anions switches from the almost exclusive formation of reversible anion-π complexes, featuring a markedly charge transfer (CT) or formal electron-transfer (ET) character, to the quantitative and irreversible net production of the anion radical [HAT(CN)(6)](•-) and the dianion [HAT(CN)(6)](2-) species. The preferred mode of interaction is dictated by the electron donor abilities of the interacting anion. Thus, weaker Lewis basic anions such as Br(-) or I(-) are prone to form mainly anion-π complexes. On the contrary, stronger Lewis basic F(-) or (-)OH anions display a net ET process. The ET process can be either thermal or photoinduced depending on the HOMO/LUMO energy difference between the electron donor (anion) and the electron acceptor (HAT(CN)(6)). These ET processes possibly involve the intermediacy of anion-π complexes having strong ET character and producing an ion-pair radical complex. We hypothesize that the irreversible dissociation of the pair of radicals forming the solvent-caged complex is caused by the reduced stability (high reactivity) of the radical resulting from the anion.

Electrochemical migration behavior of silver nanopaste screen-printed for flexible and printable electronics

Electrochemical migration (ECM) – a potential problem in confined multi-layered circuits with narrow connections – was investigated with respect to the heat treatment of silver (Ag) nanopaste screen-printed on polyimide (PI) substrates. The Ag nanopaste patterns were sintered for 30 min at various temperatures. When the sintering temperature was raised from 150 to 300 °C the Ag cluster size increased with volumetric shrinkage and the electrical resistivity decreased. ECM was evaluated by thermal humidity bias (THB) testing and water drop (WD) testing, which both showed that the Ag nanopaste sintered at higher temperatures was required longer time to bridge the adjacent Ag electrode by the ECM phenomenon. Sintering at low temperatures led to the patterned surfaces showing larger surface areas, thereby expediting the increase of electrical resistivity and hastening short circuit during THB testing. Water drop testing revealed that ECM, and associated short-circuit failure by dendrite formation between the cathode and anode, decreased with increasing sintering temperature. The dendrites were analyzed by field emission scanning electron microscope and electron probe micro analysis. The metallic dendrites, consisting of Ag oxidation products, formed as a mixture of trunk- and lace-type structures: Ag combined with H2O or OH anions to form oxides.

NIR luminescence and catalysis of multifarious salen type ytterbium complexes modulated by anions

A series of five N,N'-bis(2-hydroxy-3-methoxybenzylidene)-1,3-propanediamine (H2L) ytterbium complexes, namely, [Yb(H2L)2(CH3OH)](ClO4)3 (1), [Yb(H2L)(NO3)3]2·CH2Cl2 (2), [Yb(H2L)2(NO3)]2(PF6)4·4H2O·2CH2Cl2 (3), [Yb(H2L)(OAc)2]2(PF6)2·4CH2Cl2 (4) and [Yb3L'3(OH)2Cl(H2O)5]Cl3·4H2O (5) (HL' = 2-hydroxy-3-methoxybenzaldehyde), have been synthesized by reactions of H2L with multifarious Yb(iii) salts. X-ray diffraction analysis reveals that complex 1 shows a unique mononuclear structure constructed from two chelating H2L ligands in crossover mode. Complex 2 exhibits a dinuclear structure bridged by two H2L ligands. Complexes 3 and 4 possess two novel dinuclear structures linked by NO3(-) and OAc(-) anions, respectively. Complex 5 displays a trinuclear structure supported by three L' and two OH(-) anions. Noticeable, complex 3 can be transformed from 2 by introducing (NH4)(PF6). The PF6(-) counterion plays an essential role in steering the structural transformation. The anions dominate the final structures of 1-5. All complexes 1-5 exhibit NIR luminescence, which can be rationalized on the basis of different structural effects. Preliminary catalytic studies reveal that all complexes 1-5 are able to catalyze effectively a typical Henry reaction with good yields.