Showing papers on "Hydrogen bond published in 2020"
TL;DR: This work explains a long-standing puzzle for an important catalyst, and highlights the crucial roles of charge capacity and hydrogen bonding, which can help elucidate the mechanisms of other heterogeneous electrocatalysts in aqueous solution and enable more effective catalyst design.
Abstract: A single nickel atom embedded in graphene is one of the most representative single-atom catalysts, and it has a high activity and selectivity for electrochemical CO2 reduction (CO2R) to CO. However, the catalytic origin, especially the coordination structure of Ni, remains highly puzzling, as previous density functional theory (DFT) calculations showed that all the possible structures should be inactive and/or nonselective. Here, using ab initio molecular dynamics (AIMD) and a "slow-growth" sampling approach to evaluate the reaction kinetic barriers, we show that the charge capacity (of the site) and hydrogen bonding (with the intermediates), which were neglected/oversimplified in previous DFT calculations, play crucial roles, and including their effects can resolve the catalytic origin. Particularly, a high charge capacity allows the catalytic site to carry more charges than required for the electrochemical step, lowering the electrochemical barrier, and hydrogen bonding promotes the reaction that produces polar intermediates by stabilizing the intermediates and facilitating the H transfer from water, explaining the high selectivity for CO2R over the hydrogen evolution reaction. Consequently, we find that a hybrid coordination environment (with one nitrogen and three carbon atoms) for the Ni-atom is most active and selective for CO2R. Our work not only explains a long-standing puzzle for an important catalyst but also highlights the crucial roles of charge capacity and hydrogen bonding, which can help elucidate the mechanisms of other heterogeneous electrocatalysts in aqueous solution and enable more effective catalyst design.
173 citations
TL;DR: Density functional theory (DFT) calculations demonstrate that the recognition of aniline molecules by HOF-20 could restrict the rotation of the aromatic rings in H4BCPIA linkers, reducing the non-radiative decay pathways upon photoexcitation and subsequently enhancing the fluorescence intensity.
Abstract: A microporous three-dimensional (3D) hydrogen-bonded organic framework (HOF-20) has been constructed from an aromatic-rich tetratopic carboxylic acid, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA) The activated HOF-20a has a moderately high Brunauer-Emmett-Teller (BET) surface area of 1323 m2 g-1 and excellent stability in water and HCl aqueous solution HOF-20 exhibits highly efficient turn-up fluorescent sensing of aniline in water with a detection limit of 224 μM and is selective toward aniline in the presence of aromatic interferents, owing to the hydrogen bonding and edge-to-face π-π stacking interactions between the HOF-20 host and the guest aniline molecules, as demonstrated in the single-crystal X-ray structure of HOF-20⊃aniline Density functional theory (DFT) calculations further demonstrate that the recognition of aniline molecules by HOF-20 could restrict the rotation of the aromatic rings in H4BCPIA linkers, reducing the nonradiative decay pathways upon photoexcitation and subsequently enhancing the fluorescence intensity
131 citations
TL;DR: This investigation will shed lights into the molecular design and the electrochemical applications of a metal-organic polymer synthesized via d-π hybridization, the polymer chains of which are stitched by hydrogen bonds to feature as a robust two-dimensional (2D) layered structure.
Abstract: Organic electrode materials suffer from low electronic conductivity and poor structure stability. Herein, a metal-organic polymer, Ni-coordinated tetramino-benzoquinone (Ni-TABQ), is synthesized via d-π hybridization. The polymer chains are stitched by hydrogen bonds to feature as a robust two-dimensional (2D) layered structure. It offers both electron conduction and Na+ diffusion pathways along the directions of the polymer chains and the hydrogen bonds. With both the conjugated benzoid carbonyls and imines as the redox centers for the insertion and extraction of Na+ , the Ni-TABQ delivers high capacities of about 469.5 mAh g-1 at 100 mA g-1 and 345.4 mAh g-1 at 8 A g-1 . The large capacities are sustained for 100 cycles with almost 100 % coulombic efficiencies. The exceptional electrochemical performance is attributed to the unique 2D electron conduction and Na+ diffusion pathways enabled by the robust Ni-N and hydrogen bonds.
99 citations
TL;DR: In this paper, TpPa-1 was synthesized and exploited for radionuclides ions elimination, and the results suggest that TpPA-1 is a promising adsorbent, which is appropriate to enrichment and separation radionsides from polluted wastewater.
95 citations
TL;DR: The following article is the first attempt to investigate the supramolecular structure of cellulose with the varied moisture content by the means of Fourier-transform and near infrared spectroscopy techniques and proposed that some deconvoluted signals from the region of 3000–2750 cm−1 might be assigned to the hydroxyl group-incorporated hydrogen bonding.
Abstract: The following article is the first attempt to investigate the supramolecular structure of cellulose with the varied moisture content by the means of Fourier-transform and near infrared spectroscopy techniques. Moreover, authors aimed at the detailed and precise presentation of IR spectra interpretation approach in order to create a reliable guideline for other researchers. On the basis of obtained data, factors indicating biopolymer crystallinity and development of hydrogen interactions were calculated and the peaks representing hydrogen bonding (7500-6000 cm-1, 3700-3000 cm-1, and 1750-1550 cm-1) were resolved using the Gaussian distribution function. Then, the deconvoluted signals have been assigned to the specific interactions occurring at the supramolecular level and the hydrogen bond length, as well bonding-energy were established. Furthermore, not only was the water molecules adsorption observed, but also the possibility of the 3OH⋯O5 intramolecular hydrogen bond shortening in the wet state was found-from (27,786 ± 2) 10-5 nm to (27,770 ± 5) 10-5 nm. Additionally, it was proposed that some deconvoluted signals from the region of 3000-2750 cm-1 might be assigned to the hydroxyl group-incorporated hydrogen bonding, which is, undoubtedly, a scientific novelty as the peak was not resolved before.
90 citations
TL;DR: In this paper, three Ni(II) complexes were synthesized and characterized by physicochemical and spectroscopic methods, and the Hirshfeld surface analysis showed that the short-range forces of the hydrogen bonds in complexes 1, 2 and 3 accounted for 67.8%, 44.6% and 52.7%, respectively.
Abstract: Three Ni(II) complexes {[NiL(μ-OAc)(CH3CH2OH)]2Ni} (1), {[NiL(μ-OAc)(CH3OH)]2Ni]·2CH2Cl2·2CH3OH (2) and {[NiL(μ-OAc)(CH3OH)]2Ni}·1.5CH3OH (3) based on a Salamo-type bis-oxime ligand (H2L = 2,2′-[ethylenedioxybis(nitrilo-methylidyne)]dinaphthol) have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes 1, 2 and 3 are all trinuclear structures, and the center Ni(II) ions are six-coordinated and show the slightly distorted octahedral coordination. They all consist of three Ni(II) ions, two deprotonated L2- units, two μ-acetato ligands and two coordinated solvent molecules, as well as the crystallizing solvent molecules. Although the molecular structures of the Ni(II) complexes 1, 2 and 3 are similar to each other, obtained in different solvents, the supramolecular structures are entirely different. The complexes 1, 2 and 3 possess the self-assembled infinite 1D, 3D and 2D supramolecular structures via different intermolecular interactions (hydrogen bonds, C–H···π and π···π stacking interaction), respectively. But complex 2 formed a 3D structures by intramolecular hydrogen bonds. It is significant that the solvent molecules have obvious effects on the optical properties and molecular configuration. The Hirshfeld surface analysis showed that the short-range forces of the hydrogen bonds in complexes 1, 2 and 3 accounted for 67.8%, 44.6% and 52.7%, respectively. The molecular orbital energies for ligand H2L and complex 1 were obtained by DFT calculation, and the electron distribution, energy level and energy gap of HOMO and LUMO were given.
86 citations
TL;DR: Energy calculation and hydrogen bond analysis revealed that the van der Waals force played an important role during selective adsorption, which was confirmed by infrared spectroscopy analysis.
84 citations
TL;DR: Imine bonds and ionic hydrogen bonds dual crosslinked polybutadiene networks showed triple-shape memory effect (triple-SME), and the dual dynamic bonds offered PB networks outstanding solid-state plasticity, recyclability and self-healing behavior.
Abstract: Fabricating a single polymer network with a combination of a multi-shape memory effect (multiple-SME), solid-state plasticity, recyclability and self-healing behavior remains a challenge. We designed imine bond and ionic hydrogen bond dual cross-linked polybutadiene (PB) networks. The resulting PB networks showed a triple-shape memory effect, where imine bonds could be used to fix the permanent shape and ionic hydrogen bonds and glass transition acted as the transition segments for fixing/releasing the temporary shapes. Additionally, the dual dynamic bonds offered PB networks outstanding solid-state plasticity, recyclability and self-healing behavior. This strategy provides some insights for preparing shape memory polymers integrating multiple-SME and multi-functionality.
80 citations
TL;DR: The charge distribution analysis, which is consistent with structural analysis, indicates that the results are not impacted by changing composition, and the charge transfer observed between ions, EG and water molecules appears to be sizable.
Abstract: Ab initio molecular dynamics simulations at elevated temperature are carried out to investigate the microscopic structure of liquid mixtures (deep eutectic solvents) composed of 1:1 and 1:2 choline chloride:ethylene glycol ([Ch]Cl:EG) and 1:2:1 choline chloride:ethylene glycol:water ([Ch]Cl:EG:water). In the present study, we aim to understand the composition effect on the choline chloride:ethylene glycol deep eutectic solvent and whether there is a specific composition in these solvents with marked special behavior at the microscopic level. The role of hydrogen bonds between all components was investigated through distribution functions. The structures are governed by the balance of hydrogen bond networks and the different populations of the EG molecule conformations. In the water-containing system, water competes for association with the anion. Also, the charge distribution analysis, which is consistent with structural analysis, indicates that the results are not impacted by changing composition. In addition, the charge transfer observed between ions, EG, and water molecules appears to be significant.
79 citations
TL;DR: A hopeful perspective of the application of Li bond in Li batteries is presented, which renders a comprehensive understanding ofLi bond inLi batteries and also an outlook of its future development.
Abstract: Lithium bonds are analogous to hydrogen bonds and are therefore expected to exhibit similar characteristics and functions. Additionally, the metallic nature and large atomic radius of Li bestow the Li bond with special features. As one of the most important applications of the element, Li batteries afford emerging opportunities for the exploration of Li bond chemistry. Herein, the historical development and concept of the Li bond are reviewed, in addition to the application of Li bonds in Li batteries. In this way, a comprehensive understanding of the Li bond in Li batteries and an outlook on its future developments is presented.
79 citations
TL;DR: In this paper, the effect and mechanism of the introducing iso-propanol substituent on amine collectors were investigated by surface tension measurements, molecular dynamics simulation (MDS), and density functional theory.
TL;DR: Examination of the nature and energy of intermolecular bond interactions between thiourea and water molecules using natural bond orbital (NBO), non-linear optical (NLO), atoms in molecules (AIM), and reduced density gradient (RDG) analyses based on the quantum chemical approach and spectroscopic analysis on X-ray and FTIR found that thermodynamic parameters, polarizability, and the first hyperpolarizability increased with the number of water molecules.
Abstract: This study aims to experimentally and theoretically examine the nature and energy of intermolecular bond interactions between thiourea and water molecules using natural bond orbital (NBO), non-linear optical (NLO), atoms in molecules (AIM), and reduced density gradient (RDG) analyses based on the quantum chemical approach and spectroscopic analysis on X-ray and FTIR. Geometry optimizations of Thio-(H2O)1–5 complexes were carried out in the gas phase by B3LYP/6-311++G(d,p) level of density functional theory. The nature of the molecular interactions between the water and thiourea through hydrogen bonding has been investigated using RDG and AIM methods. NBO analysis shows that the Thio-(H2O)5 complex has higher stabilization energy values than the other complexes. The non-linear optical properties, such as dipole moment (μ), the polarizability (α0), and the first hyperpolarizability (βtot), and thermodynamic functions, such as entropy (S), specific heat capacity (Cv), and thermal energy (E), were calculated using the same method. It was observed that thermodynamic parameters, polarizability, and the first hyperpolarizability increased with the number of water molecules. X-ray diffraction analysis confirmed that thiourea is single crystal, and the thiourea/water complexes are crystalline in nature. Besides, the infrared spectrum shows the existence of water molecules and it is used to get details of the structure of the complex.
TL;DR: In this paper, a molecular dynamics approach is used to study the density distribution, dynamics properties and local structures of Na+, K+ and Cs+ ions in the vicinity of the NASH gel interface.
TL;DR: While protic ancillary groups are important in the performance of iron porphyrin ORR catalysts, it is suggested that electrostatic stabilizers of O2-bound intermediates are more crucial for cobalt porphyrs than for the corresponding cobalt complexes.
Abstract: The development and improvement of electrocatalysts for the 4H+/4e– reduction of O2 to H2O is an ongoing challenge. The addition of ancillary groups (e.g., hydrogen bonding, Bronsted acid/base) nea...
TL;DR: The three-center halogen bond of halonium ions shows distinct differences in its properties from coordinative bonds of transition metals and is therefore applicable as a complementary synthon in supramolecular chemistry.
Abstract: Due to their electron deficiency, halonium ions act as particularly strong halogen bond donors. By accepting electrons in both lobes of their empty p-orbital, they are capable of simultaneously interacting with two Lewis bases. The interaction presumes the formation of three molecular orbitals and is accordingly typically entitled as a three-center halogen bond. In analogy to the [D-H-D]+ hydrogen bonds, which are at times entitled as short and strong bonds, the [D-X-D]+ halogen bonds of halonium ions show Bondi normalized interatomic distances of 0.6-0.7 and possess both charge transfer and electrostatic characteristics. The three-center halogen bond of halonium ions shows distinct differences in its properties from coordinative bonds of transition metals and is therefore applicable as a complementary synthon in supramolecular chemistry. The three-center halogen bond modulates the reactivity of halonium ions and is hence a useful tool for synthetic organic chemistry. Following the discussion of the nature and properties of halonium ions' halogen bonds, this tutorial review provides an overview of their current applications to stimulate future developments.
TL;DR: Density functional theory calculations (DFT) reveal that the neutral molecule (NH3) in Mg(BH4)2·NH3 is exchanged between the lattice and interstitial Mg2+ facilitated by a highly flexible structure, mainly owing to a network of di-hydrogen bonds, N-Hδ+-δH-B and the versatile coordination of the BH4- ligand.
Abstract: Light weight and cheap electrolytes with fast multi-valent ion conductivity can pave the way for future high-energy density solid-state batteries, beyond the lithium-ion battery. Here we present the mechanism of Mg-ion conductivity of monoammine magnesium borohydride, Mg(BH4)2·NH3. Density functional theory calculations (DFT) reveal that the neutral molecule (NH3) in Mg(BH4)2·NH3 is exchanged between the lattice and interstitial Mg2+ facilitated by a highly flexible structure, mainly owing to a network of di-hydrogen bonds, N–Hδ+⋯−δH–B and the versatile coordination of the BH4− ligand. DFT shows that di-hydrogen bonds in inorganic matter and hydrogen bonds in bio-materials have similar bond strengths and bond lengths. As a result of the high structural flexibiliy, the Mg-ion conductivity is dramatically improved at moderate temperature, e.g. σ(Mg2+) = 3.3 × 10−4 S cm−1 at T = 80 °C for Mg(BH4)2·NH3, which is approximately 8 orders of magnitude higher than that of Mg(BH4)2. Our results may inspire a new approach for the design and discovery of unprecedented multivalent ion conductors.
TL;DR: Theoretical modeling showed that M-l-Gln assumed pH-dependent self-ordered coil conformations with main chain transoid arrangements reminiscent of the protein hairpin motif owing to intramolecular dipole moments and hydrogen bonds.
Abstract: This paper reports on synthesis, acid–base properties, and self-structuring in water of a chiral polyamidoamino acid, M-l-Gln, obtained from the polyaddition of N,N′-methylenebisacrylamide with l-glutamine, with the potential of establishing hydrogen bonds through its prim-amide pendants. The M-l-Gln showed pH-responsive circular dichroism spectra, revealing ordered conformations. Structuring was nearly insensitive to ionic strength but sensitive to denaturing agents. The NMR diffusion studies were consistent with a population of unimolecular nanoparticles thus excluding aggregation. The M-l-Gln had the highest molecular weight and hydrodynamic radius among all polyamidoamino acids described. Possibly, transient hydrogen bonds between l-glutamine molecules and M-l-Gln growing chains facilitated the polyaddition reaction. Theoretical modeling showed that M-l-Gln assumed pH-dependent self-ordered coil conformations with main chain transoid arrangements reminiscent of the protein hairpin motif owing to intramolecular dipole moments and hydrogen bonds. The latter were most numerous at the isoelectric point (pH 4.5), where they mainly involved even topologically distant main chain amide N–H and side chain amide C=O brought to proximity by structuring. Hydrogen bonds at pH 4.5 were also suggested by variable temperature NMR. The 2D NOESY experiments at pH 4.5 confirmed the formation of compact structures through the analysis of the main chain/side chain hydrogen contacts, in line with MD simulations.
TL;DR: The results showed that the amino N and amide oxygen atom were easier to provide lone pair of electrons, generating hydrogen bonds or strong electrostatic interactions with functional groups on the surface of Cc-Mt, meanwhile hydroxyl O atom was also a possible reaction site.
TL;DR: In this article, a series of 1-ethyl-3methylimidazolium ([emim]Cl)-based DASs with appropriate acidity were used to simultaneously realize efficient and reversible absorption of NH3.
Abstract: Solvents with appropriate acidity are required to simultaneously realize efficient and reversible absorption of NH3. To achieve this goal, a series of 1-ethyl-3-methylimidazolium ([emim]Cl)-based D...
TL;DR: The molecular structure, fundamental vibrational frequencies and intensities of the vibrational bands were interpreted with the aid of optimizations and normal coordinate force field calculations based on density functional theory (DFT) and ab initio HF methods with 6–311++G(d,p) basis set.
TL;DR: In this article, a new hybrid material C6H16N2(NO3)2 symbolized as follows 1EPBN ( 1 - E thyl piperazine-1,4-diium B is( N itrate)), a synergy between the two experimental and theoretical approach allows us to characterize and evaluate our crystal.
TL;DR: A fundamental study on the role of hydration on the nanostructure of a choline chloride based deep eutectic solvents, ethaline finds that at very high hydration level, chloride ion no longer acts as a bridge between the choline cation and ethylene glycol as it forms strong hydrogen bond with water.
Abstract: Recently, it has been observed that choline chloride ([Ch][Cl]) based deep eutectic solvents (DESs) may possess nanostructures in which chloride ions play a major role by providing a backbone for the bridged hydrogen bond network. In this article, we present a fundamental study on the role of hydration on the nanostructure of a [Ch][Cl] based DES, ethaline. In this molecular dynamics investigation, we observe a nonlinear change in the structural morphology of ethaline on gradual addition of water. The initiation of disruption of the native structure of the DES at 40 mol % of water is clearly observed, after which the increasing dilution rapidly destructs the long-range as well as short-range intermolecular interactions existing between the constituent species of pure ethaline. Herein, we find that, at very high hydration level, chloride ion no longer acts as a bridge between the choline cation and ethylene glycol, as it forms strong hydrogen bond with water. Intriguingly, the strengthening of hydrogen bonding interactions among the ethylene glycol molecules is observed on increasing hydration level. Hence, it is predicted that segregation of ethylene glycol can occur in the pool of aqueous mixtures of [Ch][Cl] at very high hydration level.
TL;DR: This overview features a discussion relating molecular structure to hydrogen bond strengths, highlighting the following electronic effects on hydrogen bonding: electronegativity, steric effects, electrostatic effects, π‐conjugation, and network cooperativity.
Abstract: Hydrogen bonding principles are at the core of supramolecular design. This overview features a discussion relating molecular structure to hydrogen bond strengths, highlighting the following electronic effects on hydrogen bonding: electronegativity, steric effects, electrostatic effects, π-conjugation, and network cooperativity. Historical developments, along with experimental and computational efforts, leading up to the birth of the hydrogen bond concept, the discovery of nonclassical hydrogen bonds (C-H…O, O-H…π, dihydrogen bonding), and the proposal of hydrogen bond design principles (e.g., secondary electrostatic interactions, resonance-assisted hydrogen bonding, and aromaticity effects) are outlined. Applications of hydrogen bond design principles are presented.
TL;DR: Water networks confined within zeolites solvate clustered reactive intermediates and must rearrange to accommodate transition states that differ in size and polarity, with thermodynamic penalties that depend on the shape of the confining environment.
Abstract: Aqueous-phase reactions within microporous Bronsted acids occur at active centers comprised of water-reactant-clustered hydronium ions, solvated within extended hydrogen-bonded water networks that tend to stabilize reactive intermediates and transition states differently The effects of these diverse clustered and networked structures were disentangled here by measuring turnover rates of gas-phase ethanol dehydration to diethyl ether (DEE) on H-form zeolites as water pressure was increased to the point of intrapore condensation, causing protons to become solvated in larger clusters that subsequently become solvated by extended hydrogen-bonded water networks, according to in situ IR spectra Measured first-order rate constants in ethanol quantify the stability of SN2 transition states that eliminate DEE relative to (C2H5OH)(H+)(H2O)n clusters of increasing molecularity, whose structures were respectively determined using metadynamics and ab initio molecular dynamics simulations At low water pressures (2–10 kPa H2O), rate inhibition by water (−1 reaction order) reflects the need to displace one water by ethanol in the cluster en route to the DEE-formation transition state, which resides at the periphery of water–ethanol clusters At higher water pressures (10–75 kPa H2O), water–ethanol clusters reach their maximum stable size ((C2H5OH)(H+)(H2O)4–5), and water begins to form extended hydrogen-bonded networks; concomitantly, rate inhibition by water (up to −3 reaction order) becomes stronger than expected from the molecularity of the reaction, reflecting the more extensive disruption of hydrogen bonds at DEE-formation transition states that contain an additional solvated non-polar ethyl group compared to the relevant reactant cluster, as described by non-ideal thermodynamic formalisms of reaction rates Microporous voids of different hydrophilic binding site density (Beta; varying H+ and Si–OH density) and different size and shape (Beta, MFI, TON, CHA, AEI, FAU), influence the relative extents to which intermediates and transition states disrupt their confined water networks, which manifest as different kinetic orders of inhibition at high water pressures The confinement of water within sub-nanometer spaces influences the structures and dynamics of the complexes and extended networks formed, and in turn their ability to accommodate the evolution in polarity and hydrogen-bonding capacity as reactive intermediates become transition states in Bronsted acid-catalyzed reactions
TL;DR: The later calculations prove that the studied acids have an inhibitor effect against cancer and microbial diseases and the theoretical parameters have a very good consistency with the experimental ones.
TL;DR: An effective strategy to regulate network topologies of two-dimensional (2D) covalent organic frameworks (COFs) through conformation switching of molecular linkages is proposed, which would greatly diversify the COF topologies and enable vast post-synthetic modifications like boron complexation, endowing these structures with unique optical property.
Abstract: Creating molecular networks with different topologies using identical molecular linkers is fundamentally important but requires precise chemistry control. Here, we propose an effective strategy to regulate the network topologies of two-dimensional (2D) covalent organic frameworks (COFs) through the conformational switching of molecular linkages. By simply altering the substituents of an identical molecular linker, the topology-selective synthesis of two highly crystalline 2D COFs can be readily achieved. Their distinct crystal structures are observed and determined by low-dose, high-resolution transmission electron microscopy imaging, indicating that the driving force for linkage conformation switching is intramolecular hydrogen bonding. Our strategy would greatly diversify the COF topologies and enable vast postsynthetic modifications such as boron complexation, endowing these structures with a unique optical property such as fluorescence turn on and aggregation-induced emission.
TL;DR: In this paper, the crystal structure of a novel compound (C8H14N2)2[CdCl6] denoted (MXDCdCl 6) is discussed based on single crystal X-ray diffraction.
TL;DR: In this article, a hydrazone derivative, 2-[(2,3-dimethylphenyl)amino]-N’-[(E)-thiophen-2-ylmethylidene]benzohydrazide, was synthesized and its three-dimensional structure was determined by X-ray crystallography.
TL;DR: In this article, three lanthanide compounds have been synthesized, namely, Dy2(bpda)3(H2O)3]4·2H 2O}(Dy-1), Sm 2 (Sm-2) and Tb 2 (Tb-3) (H2bpda = 2,2′-bipyridine-6,6′-dicarboxylic acid).
Abstract: Three lanthanide compounds have been synthesized, namely, {[Dy2(bpda)3(H2O)3]4·2H2O}(Dy-1), {[Sm(bpda)2·(H2O)]·H2O}n (Sm-2) and {[Tb2(bpda)3(H2O)3]4·2H2O} (Tb-3) (H2bpda = 2,2′-bipyridine-6,6′-dicarboxylic acid). Their structures were determined by single crystal X-ray diffraction and characterized by elemental analysis, infrared spectroscopy and thermogravimetric analysis. Dy-1 and Tb-3 are isostructural with a conjugate bimolecular four-nuclear cluster structure constructed with intramolecular hydrogen bonds and they form a 3D supramolecular structure with intermolecular hydrogen bonding. Sm-2 is a one-dimensional chain structure and is further connected by intricate hydrogen bonds into a three-dimensional supramolecular structure. These three compounds exhibit significant characteristic luminescence from the ligand to the central Ln(III) ion, which is found by solid-state photoluminescence measurement. Sm-2 exhibits a long luminescence lifetime and high fluorescence quantum yield. A slow relaxation phenomenon is observed for the dysprosium compound by measuring the alternating-current susceptibility at low temperature and the underlying mechanism was further confirmed by theoretical calculations.