Neighboring Oxygen Atoms Research Articles

Substantiation for Oxywater Zwitterions and Singlet Oxygen Atoms Generation from Hydrogen Peroxide Molecules in Aqueous Solutions

Hydrogen peroxide is widely used as an oxidant. The results of thermodynamic calculations indicate the impossibility of spontaneous generation of hydroxyl and hydroperoxyl radicals from hydrogen peroxide in aqueous solutions. Hydrogen peroxide spontaneously decomposes in ferrous, ferric, and cupric Fenton reaction systems. Ferric xylenol orange and ferric pyridoxine complexes are oxidized rapidly and spontaneously by this oxidant. Hydrogen peroxide in aqueous solutions spontaneously oxidizes the sulfur atoms of hyposulfite anions and benzylpenicillin molecules. Thus, a hydrogen peroxide molecule generates another intermediate that differs from hydroxyl and hydroperoxyl radicals. Theoretical modeling shows that hydrogen peroxide can participate in the proton transfer reactions. Its isomerization to oxywater zwitterion with subsequent oxywater intramolecular disproportionation is a process that is very suitable for explaining all events of hydrogen peroxide decomposition and oxidative reactivity in aqueous systems. The oxywater zwitterion is a bipolar ion in which the opposite charges are localized on neighboring oxygen atoms. This determines the displacement of electron density from the negatively charged atom to the positively charged atom. As a result, the interoxygen bond heterolytically dissociates with liberation of a water molecule and formation of an oxygen atom (oxene) in a singlet quantum state. This atom has a vacant atomic orbital. The S-oxidation of benzylpenicillin and hyposulfite occurs via targeting of electron pairs of the sulfur atoms by the vacant atomic orbitals of the singlet oxygen atoms. We substantiate an oxene-mediated pathway of hydrogen peroxide disproportionation. A singlet oxygen atom interacts with a second hydrogen peroxide molecule through targeting the unshared electron pair of the oxygen atom by a vacant atomic orbital. The process may be called O-oxidation of hydrogen peroxide; it results in trioxidane (dihydrogen trioxide) formation. Hydrogen trioxide rapidly decomposes and produces water and singlet dioxygen. We have suggested a mechanism of the electron spin rotation during the singlet dioxygen quenching into the triplet quantum state. We have assumed the formation of a dimeric associate from singlet dioxygen antipodes by orbital parameter. Two simultaneous redox reactions (the electron exchange interaction) result in generation of two triplet dioxygen molecules. The first triplet molecule has +1 total electron spin, and the second one has –1 total electron spin. For Fenton reaction systems, the zwitterionization of hydrogen peroxide in Lewis acid-base complexes with metal ions is followed by intramolecular disproportionation of oxywater. The singlet oxene remains in complex with a metal ion. Ferrous iron ion changes its oxidation state to ferric due to rapid and inevitable one-electron transfer within the iron(II)-oxene complex. The ferric-oxyl complex is known as alpha-oxygen complex. In our opinion, the classic Fenton reaction occurs through alpha-complex formation. We maintain such view that is alternative to widespread conceptions of the hydroxyl radical generation or oxoferryl(IV) formation. We have reproduced electro-Fenton reactions of transition metal ions with electrogenerated hydrogen peroxide and presumably observed voltammetric signals for the singlet oxene atoms and oxyl radical anions (alpha-oxygen particles). The oxywater-oxene concept is successfully applicable to explain the catalytic activity of redox-inactive substances. We have used our oxywater-oxene concept for explanation of hydroperoxide monooxygen and dioxygen oxidative functionalization mechanisms in organic synthesis.

Ab initio study on the structural and electronic properties of water surrounding a multifunctional nanoprobe

We report the magneto-electric behavior of a dual-modality biomedical nanoprobe, a ternary nanosystem consisting of gold and gadolinia clusters and water molecules, with the effect of both nanoclusters on the structural and electronic properties of water. The hydrogen-oxygen bond lengths and angles as well as electronic charges of water molecules surrounding both nanoclusters were calculated using Hubbard U corrected density functional theory aided by molecular dynamics approach. The calculations reveal existence of a magneto-electric interaction between gold and gadolinium oxide nanoclusters, which influences the physical properties of surrounding water remarkably. A broader (narrower) distribution of HO bond lengths (HOH bond angles) was observed at the presence of either gold or gadolinia nanoclusters. The presence of Gd6O9 cluster leads to the larger charges of neighbour oxygen atoms. The distribution of oxygen atom charges becomes border when both Gd6O9 and Au13 clusters coexist. Ab initio calculation provides a feasible approach to explore the most essential interactions among functional components of a multimodal nanoprobe applied in aqueous environment.

Proton diffusion mechanisms in the double perovskite cathode material GdBaCo2O5.5: A molecular dynamics study

GdBaCo2O5+x compounds have demonstrated to be very efficient cathode materials not only in solid oxide fuel cells but also in proton conducting fuel cells. In this last case, the excellent properties could be due to the presence of mixed electron-proton conduction. We study here the diffusion of the proton in this material using molecular dynamics simulations. Two different diffusion mechanisms are observed. The predominant mechanism is the standard proton transfer between two neighbouring oxygen atoms combined with the rotation of H around its first neighbour oxygen atom. The second mechanism consists in the migration of the OH group where both oxygen and hydrogen atoms diffuse together. Strong spatial correlations between successive proton jumps are evidenced. This is likely related to the presence of oxygen vacancies and to the concerted diffusion of hydrogen and oxygen atoms.

Deep donor state of the copper acceptor as a source of green luminescence in ZnO

Copper impurities have long been linked with green luminescence (GL) in ZnO. Copper is known to introduce an acceptor level close to the conduction band of ZnO, and the GL has conventionally been attributed to transitions involving an excited state which localizes holes on neighboring oxygen atoms. To date, a theoretical description of the optical properties of such deep centers has been difficult to achieve due to the limitations of functionals in the density functional theory. Here, we employ a screened hybrid density functional to calculate the properties of Cu in ZnO. In agreement with the experiment, we find that CuZn features an acceptor level near the conduction band of ZnO. However, we find that CuZn also gives rise to a deep donor level 0.46 eV above the valence band of ZnO; the calculated optical transitions involving this state agree well with the GL observed in ZnO:Cu.

Carbon-hydrogen defects with a neighboring oxygen atom in n-type Si

We report on the electrical activation of neutral carbon-oxygen complexes in Si by wet-chemical etching at room temperature. Two deep levels, E65 and E75, are observed by deep level transient spectroscopy in n-type Czochralski Si. The activation enthalpies of E65 and E75 are obtained as EC-0.11 eV (E65) and EC-0.13 eV (E75). The electric field dependence of their emission rates relates both levels to single acceptor states. From the analysis of the depth profiles, we conclude that the levels belong to two different defects, which contain only one hydrogen atom. A configuration is proposed, where the CH1BC defect, with hydrogen in the bond-centered position between neighboring C and Si atoms, is disturbed by interstitial oxygen in the second nearest neighbor position to substitutional carbon. The significant reduction of the CH1BC concentration in samples with high oxygen concentrations limits the use of this defect for the determination of low concentrations of substitutional carbon in Si samples.

Controlling Ag diffusion in ZnO by donor doping: A first principles study

Silver interdiffusion is often detrimental to the performance of thin-film coatings and devices that contain Ag/ZnO interfaces. Using a first principles computational analysis, a strategy is proposed which limits this diffusion by incorporating substitutional donor dopants into ZnO. First principles nudged elastic band calculations indicate that interstitial silver is likely to diffuse towards its nearby interstitial positions along [0001] in ZnO, with a relatively small energy barrier of 0.75 eV. Doping ZnO with Al slightly increases this energy barrier to 0.89 eV. In Sn-doped ZnO and Sc-doped ZnO, interstitial silver may bind to Sn or Sc and a neighbouring oxygen atom to form a Ag-O-Sn/Sc trimer in the ground state which increases the Ag migration barrier to 1.01 eV and 1.34 eV, respectively. An analysis of the Bader charges and bond strengths shows that electrostatic interactions and ionic radii have a more significant impact on Ag migration than charge transfer between the interstitial and its neighbours. In particular, the binding between Ag, O and Sn/Sc is found to be the main effect responsible for inhibiting Ag diffusion in doped ZnO.

Ordered hydroxyls on Ca3Ru2O7(001)

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is desirable to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca3Ru2O7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (Eads = 1.64 eV), forming an (OH)ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygen atom, Osurf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.

Hydroxyl-Dependent Evolution of Oxygen Vacancies Enables the Regeneration of BiOCl Photocatalyst.

Photoinduced oxygen vacancies (OVs) are widely investigated as a vital point defect in wide-band-gap semiconductors. Still, the formation mechanism of OVs remains unclear in various materials. To elucidate the formation mechanism of photoinduced OVs in bismuth oxychloride (BiOCl), we synthesized two surface hydroxyl discrete samples in light of the discovery of the significant variance of hydroxyl groups before and after UV light exposure. It is noted that OVs can be obtained easily after UV light irradiation in the sample with surface hydroxyl groups, while variable changes were observed in samples without surface hydroxyls. Density functional theory (DFT) calculations reveal that the binding energy of Bi-O is drastically influenced by surficial hydroxyl groups, which is intensely correlated to the formation of photoinduced OVs. Moreover, DFT calculations reveal that the adsorbed water molecules are energetically favored to dissociate into separate hydroxyl groups at the OV sites via proton transfer to a neighboring bridging oxygen atom, forming two bridging hydroxyl groups per initial oxygen vacancy. This result is consistent with the experimental observation that the disappearance of photoinduced OVs and the recovery of hydroxyl groups on the surface of BiOCl after exposed to a H2O(g)-rich atmosphere, and finally enables the regeneration of BiOCl photocatalyst. Here, we introduce new insights that the evolution of photoinduced OVs is dependent on surface hydroxyl groups, which will lead to the regeneration of active sites in semiconductors. This work is useful for controllable designs of defective semiconductors for applications in photocatalysis and photovoltaics.

Computational investigation of the lubrication behaviors of dioxides and disulfides of molybdenum and tungsten in vacuum

Lamellar compounds such as the disulfides of molybdenum and tungsten are widely used as additives in lubricant oils or as solid lubricants in aerospace industries. The dioxides of these two transition metals have identical microstructures with those of the disulfides. The differences in the lubrication behaviors of disulfide and dioxides were investigated theoretically. Tungsten dioxide and molybdenum dioxide exhibit higher bond strengths at the interface and lower interlayer interactions than those of the disulfides which indicates their superlubricity. Furthermore, the topography of the electron density of the single layer nanostructure determined their sliding potential barrier; the dioxides showed a weaker electronic cloud distribution between the two neighboring oxygen atoms, which facilitated the oxygen atoms of the counterpart to go through. For commensurate friction, the dioxides exhibited nearly the same value of friction work, and same was the case for the disulfides. The lower positive value of friction work for the dioxides confirmed their improved lubricity than the disulfides and the higher mechanical strength of the bulk dioxides demonstrated that they are excellent solid lubricants in vacuum.

Insights on molecular structure and micro-properties of alkali-activated slag materials: A reactive molecular dynamics study

The material design of the alkali activated slag (AAS) contributes to the development of the sustainable “Green Building Materials” for the recycle of industrial waste and energy reservation of cement materials production. A computational simulation technique based on reactive molecular dynamics proposed a new view of molecular structure for the main hydrate, C-A-S-H gel, in AAS. In this paper, structure, dynamics and mechanical properties of C-A-S-H gel have been investigated. The proposed C-A-S-H model exhibits heterogeneity layered features with ordered and stable atomistic arrangement in the calcium sheets and disordered chemical connections in the interlayer region. Structurally, Al atoms bridge the neighboring oxygen atoms in the defective silicate chains, contributing to the polymerization of the C-A-S-H gel. The increase of Al or Si can significantly enhance the mean silicate chain length of the structure, and the introduction of Al atoms in the interlayer region can improve the mechanical properties of the C-A-S-H gel. Therefore, the mean chain length can be taken as important parameter to guide the high performance AAS materials design.

Ho3+-Yb3+ codoped tellurite based glasses in visible lasers and optical devices: Judd-Ofelt analysis and frequency upconversion

The optical absorption and frequency upconversion emission in the Ho3+/Yb3+ codoped TeO2-ZnO (TZ), TeO2-ZnO-WO3 (TZW) and TeO2-ZnO-WO3-TiO2 (TZWTi) glasses prepared by melting and quenching method has been studied. Judd-Ofelt theory has been used to calculate the Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6), transition probabilities, radiative lifetimes, absorption cross sections and the branching ratios. Upconversion (UC) emission bands centered at ∼ 549 nm, ∼658 nm and ∼754 nm are observed upon 980 nm excitation. On codoping with the Yb3+ ions at 3.0 mol% the upconversion emission intensity enhancement of about ∼57 times, ∼342 times and ∼480 times for the green band whereas for the red band arising from the Ho3+ ions it is about ∼71 times, ∼438 times and ∼707 times respectively have been observed. The enhancement observed in the UC emission intensity is explained on the basis of efficient energy transfer from Yb3+ to Ho3+, larger absorption cross section, larger oscillator strengths and increase in the local field corrections factor. The spectroscopic quality factor Ω4/Ω6 has been calculated to get the information about the developed materials for laser applications. The upconversion emission cross section determined on the basis of Judd-Ofelt analysis is found to be maximum for Ho-Yb-TZWTi glass. The nephelauxetic ratio, bonding and covalency parameters have been calculated to know the nature of bonding between the rare earth ions and neighbouring oxygen atoms. The high color purity 83.8% has been reported in the codoped glasses at ∼81.2 W/cm2 pump power density.

Synthesis, vibrational spectroscopic investigations, molecular docking, antibacterial studies and molecular dynamics study of 5-[(4-nitrophenyl)acetamido]-2-(4-tert-butylphenyl)benzoxazole

Antimicrobial active 5-[(4-nitrophenyl)acetamido]-2-(4-tert-butylphenyl)benzoxazole (NATPB) was synthesized and observed IR, Raman bands are compared with the theoretically predicted wave numbers. In the IR spectrum the NH stretching wave number splits into a doublet with a noted difference and is red shifted from the computed value, which indicates the weakening of NH bond resulting in proton transfer to the neighbouring oxygen atom. The HOMO-LUMO plots reveal the charge transfer in the molecular system through the conjugated paths. The electrophilic and nucleophilic reactive sites are identified from the MEP plot. Mapping of average local ionization energy (ALIE) values to the electron density surface served us as a tool for prediction of molecule sites possibly prone to electrophilic attacks. Other important reactive centres of the title molecule were detected by calculations of Fukui functions. Calculations of bond dissociation energies (BDE) for hydrogen abstraction were used in order to assess whether the NATPB molecules is prone to autoxidation mechanism or not, while BDE of the remaining single acyclic bonds were used in order to determine the weakest bond. Interaction properties with water were investigated by molecular dynamics (MD) simulations and calculations of radial distribution functions (RDFs). The compound possessed broad spectrum activity against all of the tested Gram-positive and Gram-negative bacteria and yeasts, their minimum inhibitory concentrations (MICs) ranging between 32 and 128 μg/ml. The compound exhibited significant antibacterial activity (32 μg/ml) against an antibiotic resistant E. faecalis isolate, at same potency with the compared standard drugs vancomycin and gentamycin sulfate. The molecular docking studies show that the compound might exhibit inhibitory activity against CDK inhibitors.

Enhanced frequency upconversion and non-colour tunability in Er3+–Yb3+ codoped TeO2–WO3–Pb3O4 glasses

TeO2–WO3–Pb3O4 glasses codoped with Er3+–Yb3+ ions have been prepared by melting and quenching process. Judd–Ofelt analysis has been performed to calculate the various radiative parameters viz., radiative lifetime, branching ratio and stimulated emission crosssections by using the absorption spectra. The nephelauxetic ratio, bonding and covalency parameters have been determined to get the information about the nature of bonding between the rare earth ions and neighbouring oxygen atoms. The near infrared (NIR) to visible frequency upconversion (UC) study upon excitations with 980 nm and 808 nm diode lasers has been performed. The variations observed in the UC emission intensity arising from the Er3+ ions have been explained on the basis of efficient energy transfer Yb3+ → Er3+ ions and back energy transfer Er3+ → Yb3+ processes. On codoping with Yb3+ ions the intensity of the UC emission bands observed in the codoped glass upon excitation at 980 nm has been enhanced by many folds and explained on the basis of the oscillator strengths, UC emission crosssection and temporal evolution analysis. No tuning in the colour emitted from the codoped glass upon excitation at 980 nm is reported. The results suggested that the codoped glass may be suitable in making the NIR to visible upconverter and colour non-tunable optical devices.

Spectroscopic, quantum chemical studies, Fukui functions, in vitro antiviral activity and molecular docking of 5-chloro-N-(3-nitrophenyl)pyrazine-2-carboxamide

The molecular structural parameters and vibrational frequencies of 5-chloro-N-(3-nitrophenyl)pyrazine-2-carboxamide have been obtained using density functional theory technique in the B3LYP approximation and CC-pVDZ (5D, 7F) basis set. Detailed vibrational assignments of observed FT-IR and FT-Raman bands have been proposed on the basis of potential energy distribution and most of the modes have wavenumbers in the expected range. In the present case, the NH stretching mode is a doublet in the IR spectrum with a difference of 138 cm−1 and is red shifted by 76 cm−1 from the computed value, which indicates the weakening of NH bond resulting in proton transfer to the neighboring oxygen atom. The molecular electrostatic potential has been mapped for predicting sites and relative reactivities towards electrophilic and nucleophilic attack. The hyperpolarizability values are calculated in order to find its role in nonlinear optics. From the molecular docking study, amino acids Asn161, His162 forms H-bond with pyrazine ring and Trp184, Gln19 shows H-bond with CO group and the docked ligand, title compound forms a stable complex with cathepsin K and the results suggest that the compound might exhibit inhibitory activity against cathepsin K. Moderate in vitro antiviral activity with EC50 at tens of μM was detected against feline herpes virus, coxsackie virus B4, and influenza A/H1N1 and A/H3N2.

Alkali Ion Incorporation into V2O5: a Noncovalent Interactions Analysis

Understanding the interaction of alkali metals with layered materials like vanadia is important for a range of technological applications such as energy storage and heterogeneous catalysis. Here we used the NCI (noncovalent interactions) index to analyze the nature of the chemical bonding between inserted alkali atoms (Li, Na, and K) and vanadia. We found that alkali atoms ionize in bulk vanadia making directional ionic bonds with neighboring oxygen atoms, whereas the dispersive interactions between vanadia layers remain unmodified by the presence of alkali ions. Interestingly, we show how the NCI analysis discriminates among the different vanadium–oxygen types of bond, capturing even finer interactions involving reduced vanadium sites or ring stabilization. In addition, we explored dynamic effects, concluding that the directionality of all interactions is preserved at 500 K.

A combined computational and experimental investigation of Mg doped α-Fe2O3.

In the current work, pristine α-Fe2O3 metal oxide was doped with Mg in an attempt to modulate its electronic properties. To this end, we employed an experimental high throughput strategy, including scanning XRD and optical spectroscopy, which were complimented by atomistic density functional theory (DFT) calculations. The combined study reveals that at Mg/Fe atomic ratios up to ∼1/3, the bandgaps of the hematite-Mg composite materials are similar to that of the pure material. The observed bandgaps are rationalized by electronic band structure and density of states calculations. Additional rationale for the similar bandgaps in pure and doped hematite is provided by topological Bader charge analyses, which indicate that the Mg and Fe ions in the hematite matrix have similar partial atomic charges. Nonetheless, the small charge density difference between the Mg and Fe ions induces a slight spin polarization on both oxygen and Fe ions, resulting in changes in the band edges. Further charge density analyses, using charge density maps and chemical-bonding analyses with the crystal orbital Hamiltonian population scheme, indicate that Mg forms ionic bonds with the neighboring oxygen atoms. This change from iron-oxygen covalent bonds to a more ionic nature for magnesium-oxygen bonds is probably responsible for the reduction observed in the computed bulk modulus of α-Mg(0.17)Fe(1.83)O3 (193 GPa) compared to α-Fe2O3 (202 GPa).

Interfacial interaction of Ag nanoparticles with graphene oxide supports for improving NH3 and NO adsorption: a first-principles study.

We investigated the structural and electronic properties of Ag13 nanoparticles (NPs) deposited on graphene oxides (GOs) and the effect of the interfacial interaction on NH3 and NO adsorption using density functional theory calculations. The epoxy functional group and its neighboring sp(2) carbon atoms of GOs, rather than the hydroxyl group, are used as active sites to enhance the binding of Ag13 to graphene through the C-O-Ag and C-Ag chemical bonds. The stability of deposited Ag NPs depends on the chemical environment of active sites in GOs, including the atomic arrangement of epoxides and their concentration. The deposited Ag13 NPs are likely to be further oxidized to form Ag13O by neighboring oxygen irrespective of the oxidation level of GOs. The strong interfacial interaction of Ag13/GOs, which effectively tunes the position of the d-band center of NPs due to large charge transfer from Ag13 to GOs, has a significant impact on the adsorption of NH3. The NH3 is strongly adsorbed on deposited Ag13 through the formation of an N-Ag bond and an N···HO hydrogen bond between NH3 and O from C-O-Ag. The electronic structure calculations show that the hybridization of the HOMO of NH3 with the conduction bands of Ag13-GOs results in the strong donor doping by an NH3 molecule, and gives rise to larger charge transfers from NH3 to the hybrid, compared to NH3 adsorption on isolated Ag13 and GOs. The adsorption of NO on oxidized Ag13 on GOs is obviously improved due to the oxidation of NO to NO2 by its neighboring oxygen atoms. In contrast to NH3, the adsorbed NO acts as an acceptor. The calculated results show good agreement with experimental observations.

High-energy resolution X-ray absorption and emission spectroscopy reveals insight into unique selectivity of La-based nanoparticles for CO2

The lanthanum-based materials, due to their layered structure and f-electron configuration, are relevant for electrochemical application. Particularly, La2O2CO3 shows a prominent chemoresistive response to CO2. However, surprisingly less is known about its atomic and electronic structure and electrochemically significant sites and therefore, its structure-functions relationships have yet to be established. Here we determine the position of the different constituents within the unit cell of monoclinic La2O2CO3 and use this information to interpret in situ high-energy resolution fluorescence-detected (HERFD) X-ray absorption near-edge structure (XANES) and valence-to-core X-ray emission spectroscopy (vtc XES). Compared with La(OH)3 or previously known hexagonal La2O2CO3 structures, La in the monoclinic unit cell has a much lower number of neighboring oxygen atoms, which is manifested in the whiteline broadening in XANES spectra. Such a superior sensitivity to subtle changes is given by HERFD method, which is essential for in situ studying of the interaction with CO2. Here, we study La2O2CO3-based sensors in real operando conditions at 250 °C in the presence of oxygen and water vapors. We identify that the distribution of unoccupied La d-states and occupied O p- and La d-states changes during CO2 chemoresistive sensing of La2O2CO3. The correlation between these spectroscopic findings with electrical resistance measurements leads to a more comprehensive understanding of the selective adsorption at La site and may enable the design of new materials for CO2 electrochemical applications.

Exploring the Single Atom Spin State by Electron Spectroscopy

To control the spin state of an individual atom is an ultimate goal for spintronics. A single atom magnet, which may lead to a supercapacity memory device if realized, requires the high-spin state of an isolated individual atom. Here, we demonstrate the realization of well isolated transition metal (TM) atoms fixed at atomic defects sparsely dispersed in graphene. Core-level electron spectroscopy clearly reveals the high-spin state of the individual TM atoms at the divacancy or edge of the graphene layer. We also show for the first time that the spin state of single TM atoms systematically varies with the coordination of neighboring nitrogen or oxygen atoms. These structures can be thus regarded as the smallest components of spintronic devices with controlled magnetic behavior.

Rigidity versus Flexibility of Ligands in the Assembly of Entangled Coordination Polymers Based on Bi- and Tetra Carboxylates and N-Donor Ligands

Seven Zn(II) coordination polymers including [Zn(pbda)(p-bimb)]·H2O (1), [Zn(pbda)(bpa)0.5] (2), [Zn(pbda)(bpp)] (3), [Zn(Hpbda)2(bibm)2] (4), [Zn(pbta)0.5(m-bimb)]·H2O (5), [Zn(pbta)0.5(bpp)(H2O)] (6), and [Zn(H2pbta)(bibm)]·H2O (7) (H2pbda = 4,4′-{[1,4-phenylenebis(methylene)]bis(oxy)}dibenzoic acid; p-bimb = 1,4-bis(1H-imidazol-l-yl)methyl)benzene; bpa = 1,2-bis(4-pyridyl)ethane; bpp = 1,3-bis(4-pyridyl)-propane; bibm = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl; m-bimb = 1,3-bis(1H-imidazol-l-yl)methyl)-benzene; H4pbta = 5,5′-phenylenebis(methylene)-1,1′-3,3′-(benzene-tetracarboxylic acid) were prepared under solvothermal conditions and structurally characterized. Compound 1 shows a three-dimensional (3D) channel-like architecture constructed by helical chain subunits. Compound 2 shows a rare 2D + 2D + 2D → 2D network with both polyrotaxane and polycatenane features. 3 holds a 2D layer structure constituted of metal-sharing right- and left-handed helical chains. Compound 4 presents a one-dimensional (1D) chain which is decorated by long side arms around the chain. Compound 5 possesses a 2D wave-like layer formed by [Zn2(m-bimb)]n chains by linear pbta ligands. Compound 6 displays a 3D framework that is stabilized by hydrogen bonding interactions between the coordinated H2O molecules and the neighboring carboxylate oxygen atoms. Compound 7 possesses a 1D + 1D → 2D polycatenation motif. The results demonstrated that the rigidity versus flexibility of the ligands along with the number of carboxyl groups make an impact on the structural diversities of the entangled coordination polymers. Moreover, compounds 3 and 6 as representative examples possessed high catalytic efficiency for the photodecomposition of methyl blue in water using natural sunlight irradiation.