Neutral Monomer Research Articles

Charge Delocalization through Benzene, Naphthalene, and Anthracene Bridges in π-Conjugated Oligomers: An Experimental and Quantum Chemical Study

To understand the influence of orthogonal conjugation pathways fused directly to π-conjugated polymer backbones, we synthesized and studied three series of thiophene-based model compounds containing benzene, naphthalene, and anthracene peri-substituted central cores as representative acenes. These models were functionalized with methyl groups at the reactive thiophene positions in order to generate and observe oxidized species without complications from follow-up polymerization. The neutral monomers and their oxidized charged counterparts were subjected to cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy as appropriate, and these results were further corroborated with thorough density functional theory studies. This joint experimental and theoretical analysis allowed us to determine that benzene-based conjugated linkers led to more delocalized charge carriers on account of the quinoidal character maintained within the benzene core. In contrast, anthracene-based linkers displayed very localized carriers due to torsional strain between the adjacent aryl groups and to the local evolution of formal aromatic sextets on the benzo-fused rings orthogonal to the backbone in the quinoidal state. In some cases, the electronics of the thiophene-based substituent dominated the electronic properties of the oxidized species regardless of the nature of the central acene linker. These results highlight the dramatic influence that orthogonal conjugation pathways can exert on the electronic properties of π-conjugated materials.

Preparation and evaluation of a hydrophilic poly(2‐hydroxyethyl methacrylate‐co‐N,N′‐methylene bisacrylamide) monolithic column for pressurized capillary electrochromatography

A polar polymethacrylate-based monolithic column was introduced and evaluated as a hydrophilic interaction CEC stationary phase. The monolithic stationary phase was prepared by in situ copolymerization of a neutral monomer 2-hydroxyethyl methacrylate and a polar cross-linker N,N'-methylene bisacrylamide in a binary porogenic solvent consisting of dodecyl alcohol and toluene. The hydroxyl and amino groups at the surface of the monolithic stationary phase provided polar sites which were responsible for hydrophilic interactions. The composition and proportion of the polymerization mixture was investigated in detail. The mechanical stability and reproducibility of the obtained monolithic column preformed was satisfied. The effects of pH and organic solvent content on the EOF and the separation of amines, nucleosides, and narcotics on the optimized monolithic column were investigated. A typical hydrophilic interaction CEC was observed on the neutral polar stationary phase. The optimized monolithic column can obtain high-column efficiencies with 62,000-126,000 theoretical plates/m and the RSDs of column-to-column (n = 9), run-to-run (n = 5), and day-to-day (n = 3) reproducibility were less than 6.3%. The calibration curves of these five narcotics exhibited good linearity with R in the range of 0.9959-0.9970 and linear ranges of 1.0-200.0 μg/mL. The detection limits at S/N = 3 were between 0.2 and 1.2 μg/mL. The recoveries of the separation of narcotics on the column were in the range of 84.0-108.6%. The good mechanical stability, reproducibility, and quantitation capacity was suitable for pressure-assisted CEC applications.

Single-step synthesis of polypyrrole nanowires by cathodic electropolymerization

Polypyrrole nanowires are successfully fabricated with a one-step process by cathodic electropolymerization from an aqueous solution without templates and chemical additives. The method utilizes electrochemically generated NO+ to oxidize the neutral pyrrole monomers, making it possible to use oxidizable metal substrates, such as Cu and Ni. The synthesized nanowires are directly deposited on the substrate in the form of a thin film consisting of fine polypyrrole nanowires with a nanoporous and interconnected network structure. The growth kinetics of the polypyrrole nanowires was investigated by analyzing the effects of the chemical composition of the electrolyte and the synthesis time on the formation of polypyrrole nanowires. It was found that the polymerization process of pyrrole is very sensitive to the reactivity of radical cations. For a radical cation with high reactivity, the polypyrrole nanospheres are synthesized near the electrode in the solution. In contrast, for a radical cation with sufficiently low reactivity, the polypyrrole nanowires are grown on the priorly deposited polypyrrole nanospheres.

Precisely Controlled Smart Polymer Scaffold for Nanoscale Manipulation of Biomolecules

We demonstrate the application of a novel smart surface to modulate the orientation of immobilized double stranded DNA (dsDNA) and the conformation of a polymer scaffold through variation in buffer pH and ionic strength. An amphoteric poly(dimethylacrylamide) based coating containing weak acrylamido acids and bases, which are copolymerized together with the neutral monomer, is covalently bound to the surface. The coating can be made to contain any desired amount of buffering and titrant ionogenic monomers, allowing control of the surface charge when the surface is bathed in a given buffer pH. Spectral self-interference fluorescence microscopy (SSFM) is utilized to precisely quantify both the DNA orientation and the polymer conformation with subnanometer resolution. It is possible to utilize the polymer scaffold to functionalize a variety of common materials used in microfabrication, making it a general purpose building block for the next generation of nanomachines and biosensors.

Novel polyelectrolyte gels as absorbent polymers for nonpolar organic solvents based on polymerizable ionic liquids

Novel class of polyelectrolyte gels based on the copolymer of vinylimidazolium-typed ionic liquid monomer and Dodecyl methacrylate was prepared by free radical polymerization. A small amount of 3-n-Dodecyl-1-vinylimidazolium tetrafluoroborate is incorporated into crosslinked polyacrylates to provide new lipophilic polyelectrolyte gels that evaluated for swelling in less-polar and nonpolar organic solvents. Their swelling degree becomes more than 50 times as much as their dried weights in some organic solvents. By varying the polarity of the neutral monomer in these polyelectrolyte gels, the design of gels that can absorb solvents of nearly any polarity is demonstrated. The present absorbents are expected to find practical applications particularly in the recovery of spilled oils and the treatment of waste water.

The role of lignin for the δ13C signature in C4 grassland and C3 forest soils

13C contents of organic matter are changing during decomposition of plant material and stabilization as soil organic carbon (SOC). In this context, several studies showed 13C enrichment in soil as compared to vegetation for C3 forests, whereas depletion of 13C was frequently reported for C4 grassland soil as compared to C4 vegetation. These changes were often attributed to selective preservation and/or stabilization of specific organic compounds. This study investigates if changes in the chemical composition of OC and specifically lignin may explain the observed shifts in δ13C values from plant material to SOC. We analyzed aboveground biomass, roots and heavy organo-mineral fractions from topsoils in both, long-term stable C4 grasslands and C3 Araucaria forest situated nearby in the southern Brazilian highlands on soils with andic properties. The stable carbon isotope (12C/13C) composition was analyzed for total organic carbon (OCtot) and lignin-derived phenols. The bulk chemical composition of OC was assessed by solid-state 13C NMR spectroscopy while neutral sugar monomers were determined after acid hydrolysis. The shifts of the 13C/12C isotope signature during decomposition and stabilization (plant tissues versus soil heavy fractions) showed similar trends for VSC phenols and OCtot (13C depletion in C4 grassland soil and 13C enrichment in C3 forest soil compared to the corresponding vegetation). In this regard, the isotopic difference between roots and aboveground biomass was not relevant, but may become more important at greater soil depths. 13C depletion of VSC lignins relative to OCtot was higher in C3-biomass and C3-derived SOC compared to the C4 counterparts. As lignin contents of heavy fractions were low, in particular for those with C4 isotopic signature, the influence of lignin on OCtot δ13C values in grassland topsoils is presumably low. Rather, the presence of charred grass residues and the accumulation of alkyl C in heavy fractions as revealed by 13C NMR spectroscopy contribute to decreasing δ13C values from grass biomass to C4-derived heavy fractions. In forest topsoils, the accumulation of 13C depleted VSC lignin residues in heavy fractions counteracts the prevailing 13C enrichment of OCtot from plant biomass to heavy fractions. Nonetheless, non-lignin compounds with relatively high 13C contents like microbial-derived OC have a stronger influence on δ13C values of OCtot in forest soils than lignins or aliphatic biopolymers. The mineral-associated SOC is in a late phase of decomposition with large contributions of microbial-derived carbohydrates, but distinct structural and isotopical alterations of lignin between C4- and C3-derived heavy fractions. This may indicate different processes and/or extent of lignin (and SOM) biodegradation between C4 grassland and C3 forest resulting from other kind of decomposer communities in association with distinct types and amounts of plant input as source of SOM and thus, carbon source for microbial transformation. Our results indicate that the importance of lignin for δ13C values of OCtot was overestimated in previous studies, at least in subtropical C4 grassland and C3 forest topsoils.

Collisional activation of [14Pro+2H]2+ clusters: chiral dependence of evaporation and fission processes.

Ion mobility/mass spectrometry techniques are used to investigate the dissociation of the small proline cluster [14Pro+2H](2+) produced by electrospray ionization. While this cluster is known to prefer heterochiral compositions (i.e., mixed L- and D-compositions, J. Phys. Chem. A, submitted for publication), it is possible to produce homochiral forms by electrospraying solutions containing only L- or D-proline. Differences in the measured cross sections for [14Pro+2H](2+) produced from enantiomerically pure (100% l or 100% d) or racemic (50:50 l/d) solutions indicate that homochiral and heterochiral clusters have different structures. Upon low-energy collisional activation, both the heterochiral and homochiral doubly charged structures evaporate neutral proline monomers, resulting in the formation of [xPro+2H](2+) ions (where x = 9-13). At higher activation energies, there is evidence that these smaller clusters (primarily [10Pro+2H](2+)) fission to produce [xPro+H](+) (where x = 1-6). Analysis of product ion intensities reveals a strong chiral preference associated with fissioning. Products of evaporation also show a chiral dependence but to a lesser extent.

Mechanism for translocation of fluoroquinolones across lipid membranes

Classical atom-scale molecular dynamics simulations, constrained free energy calculations, and quantum mechanical (QM) calculations are employed to study the diffusive translocation of ciprofloxacin (CPFX) across lipid membranes. CPFX is considered here as a representative of the fluoroquinolone antibiotics class. Neutral and zwitterionic CPFX coexist at physiological pH, with the latter being predominant. Simulations reveal that only the neutral form permeates the bilayer, and it does so through a novel mechanism that involves dissolution of concerted stacks of zwitterionic ciprofloxacins. Subsequent QM analysis of the observed molecular stacking shows the important role of partial charge neutralization in the stacks, highlighting how the zwitterionic form of the drug is neutralized for translocation. The findings propose a translocation mechanism in which zwitterionic CPFX molecules approach the membrane in stacks, but they diffuse through the membrane as neutral CPFX monomers due to intermolecular transfer of protons favored by partial solvation loss. The mechanism is expected to be of importance in the permeation and translocation of a variety of ampholitic drugs with stacking tendencies.

Cationic Copolyelectrolytes: Online Monitoring of the Synthesis and Subsequent Copolymer Characterization

AbstractKinetics of copolymerization reactions of diallyldimethylammonium chloride (DADMAC) and dimethyl acrylamide (DMA) in aqueous solvent is studied, with highlights on features that control many aspects of the polymeric materials behavior throughout and post‐synthesis. The aim of this study is twofold; first, to offer a method to study the impact of the incorporation of the cationic DADMAC on the composition drift, molecular mass of the copolyelectrolyte, and on the polyelectrolyte behavior by monitoring in real time the copolymerization reactions with a neutral monomer under different conditions. Additionally, it is meant to make the transition toward the next step, controlling the reaction kinetics during designed semi‐batch experiments designed to achieve the average mass and composition distributions desired.

Trans-Diaquabis(1Himidazolium-4,5-dicarboxylato-κ2O4,O5)magnesium

The title compound, [Mg(C5H3N2O4)2(H2O)2], consists of centrosymmetric neutral monomers in which two O,O′-bidentate imidazolinium-4,5-dicarboxyl­ate ligands are bonded to the MgII ion. One of the carboxyl protons is transferred to the N atom of the imidazole ring. The octa­hedral metal-ion coordination is completed by two trans water O atoms. In the crystal, mol­ecules are linked by N—H⋯(O,O) and O—H⋯O hydrogen bonds.

Modeling of particle generation in laser ablation plasma

In this study, we used the general dynamic equation (GDE) for aerosols, combined with particle charging by positive ions and electrons, to simulate particle generation in laser ablation plasmas. The population balance equations based on Brownian coagulation and diffusion charging theory were represented by using a discrete-sectional model. The temporal evolution of the particle size distribution was simulated at three different initial number concentrations of neutral monomers, positive ions and electrons, as well as at two different gas pressures.The simulated average particle size increased with time and with increasing initial concentration of neutral monomer and gas pressure. The particle growth was affected by the particle charging when both number ratios of positive ion to neutral monomer and of electron to neutral monomer are higher than 0.1. Simulated particle size distributions were compared with SEM images of particles collected at different sampling points and gas pressures in actual plasmas operating at conditions similar to those simulated. Changes of particle size with increasing distance between the target and the sampling point and with increasing the pressure were well reproduced by simulations. However, particle diameters calculated were much smaller than SEM images because physical values, such as, initial concentrations of monomer, positive ions and electrons and the recombination probability of electron and positive ions, used in calculations were invalid.

Clay fractions from a soil chronosequence after glacier retreat reveal the initial evolution of organo–mineral associations

Interactions between organic and mineral constituents prolong the residence time of organic matter in soils. However, the structural organization and mechanisms of organic coverage on mineral surfaces as well as their development with time are still unclear. We used clay fractions from a soil chronosequence (15, 75 and 120years) in the foreland of the retreating Damma glacier (Switzerland) and from mature soils outside the proglacial area (>700 and <3000years) to elucidate the evolution of organo–mineral associations during initial soil formation. The chemical composition of the clay-bound organic matter (OM) was assessed by solid-state 13C NMR spectroscopy while the quantities of amino acids and neutral sugar monomers were determined after acid hydrolysis. The mineral phase was characterized by X-ray diffraction, oxalate extraction, specific surface area by N2 adsorption (BET approach), and cation exchange capacity at pH 7 (CECpH7). The last two methods were applied before and after H2O2 treatment. We found pronounced shifts in quantity and quality of OM during aging of the clay fractions, especially within the first one hundred years of soil formation. The strongly increasing organic carbon (OC) loading of clay-sized particles resulted in decreasing specific surface areas (SSA) of the mineral phases and increasing CECpH7. Thus, OC accumulation was faster than the supply of mineral surfaces and cation exchange capacity was mainly determined by the OC content. Clay-bound OC of the 15-year-old soils showed high proportions of carboxyl C and aromatic C. This may point to remnants of ancient OC which were inherited from the recently exposed glacial till. With increasing age (75 and 120years), the relative proportions of carboxyl and aromatic C decreased. This was associated with increasing O-alkyl C proportions, whereas accumulation of alkyl C was mainly detected in clay fractions from the mature soils. These findings from solid-state 13C NMR spectroscopy are in line with the increasing amounts of microbial-derived carbohydrates with soil age. The large accumulation of proteins, which was comparable to those of carbohydrates, and the very low C/N ratios of H2O2-resistant OM indicated strong and preferential associations between proteinaceous compounds and mineral surfaces. In the acid soils, poorly crystalline Fe oxides were the main providers of mineral surface area and important for the stabilization of OM during aging of the clay fractions. This was indicated by (I) the strong correlations between oxalate soluble Fe and both, SSA of H2O2-treated clay fractions and OC content, and (II) the low formation of expandable clays due to small extents of mineral weathering. Our chronosequence approach provided new insights into the evolution of organo–mineral interactions in acid soils. The formation of organo–mineral associations started with the sorption of proteinaceous compounds and microbial-derived carbohydrates on mineral surfaces which were mainly provided by ferrihydrite. The sequential accumulation of different organic compounds and the large OC loadings point to multiple accretion of OM in distinct zones or layers during the initial evolution of clay fractions.

Transesterification of functional methacrylate monomers during alcoholic copper-catalyzed atom transfer radical polymerization: formation of compositional and architectural side products

Neutral methacrylate monomers undergo transesterification in methanol to produce multiple by-products under copper-catalyzed atom transfer radical polymerization (ATRP) conditions. The side-reactions occur for a range of hydrophilic methacrylates but some may be reduced by employing higher alcohols. This study demonstrates that care must be taken when using alcohol solvents for the synthesis of architecturally and compositionally pure methacrylate (co)polymers via copper-catalyzed conventional ATRP.

Evaluation of the corrosion protection behaviour of poly(neutral red) films on passivated copper

The corrosion protection behaviour of poly(neutral red) (PNR) films on copper electrodes has been investigated using open circuit measurements, Tafel plots and electrochemical impedance spectroscopy. Pure copper electrodes were initially passivated in sodium oxalate, salicylate or hydrogen carbonate solution, to inhibit copper dissolution at potentials where neutral red monomer oxidation occurs, before its electropolymerization by potential cycling. The corrosion inhibition by these films was tested in 0.10 M KCl solution. It was found that, after long immersion times (96 h), the best protection efficiency was with PNR films formed on copper passivated in oxalate solution.

Synthesis of Molecularly Imprinted Polymers for Amino Acid Derivates by Using Different Functional Monomers

Fmoc-3-nitrotyrosine (Fmoc-3-NT) molecularly imprinted polymers (MIPs) were synthesized to understand the influence of several functional monomers on the efficiency of the molecular imprinting process. Acidic, neutral and basic functional monomers, such as acrylic acid (AA), methacrylic acid (MAA), methacrylamide (MAM), 2-vinylpyridine (2-VP), 4-vinylpyridine (4-VP), have been used to synthesize five different polymers. In this study, the MIPs were tested in batch experiments by UV-visible spectroscopy in order to evaluate their binding properties. The MIP prepared with 2-VP exhibited the highest binding affinity for Fmoc-3NT, for which Scatchard analysis the highest association constant (2.49 × 104 M−1) was obtained. Furthermore, titration experiments of Fmoc-3NT into acetonitrile solutions of 2-VP revealed a stronger bond to the template, such that a total interaction is observed. Non-imprinted polymers as control were prepared and showed no binding affinities for Fmoc-3NT. The results are indicative of the importance of ionic bonds formed between the –OH residues of the template molecule and the pyridinyl groups of the polymer matrix. In conclusion, 2-VP assists to create a cavity which allows better access to the analytes.

Photoionization of epichlorohydrin enantiomers and clusters studied with circularly polarized vacuum ultraviolet radiation

The photoionization of enantiomerically pure epichlorohydrin (C(3)H(5)OCl) has been studied using linearly and circularly polarized vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum was recorded and the first three bands assigned using molecular orbital calculations for the expected conformers, although uncertain experimental conformer populations and an anticipated breakdown in Koopmans' theorem leave some ambiguity. Measurements of the photoelectron circular dichroism (PECD) were obtained across a range of photon energies for each of these bands, using electron velocity map imaging to record the angular distributions, during which a record PECD chiral asymmetry factor of 32% was observed. A comparison with calculated PECD curves clarifies the assignment achieved using ionization energies alone and further suggests a likely relative population of the conformers. Threshold photoelectron-photoion coincidence methods were used to study the ionic fragmentation of epichlorohydrin. Fragment ion appearance energies show nonstatistical behavior with clear indications that the cationic epoxide ring is unstable and lower energy decay channels proceeding via ring breaking are generally open. Extensive neutral homochiral clusters of epichlorohydrin may be formed in supersonic molecular beam expansions seeded in Ar. Electron angular distribution measurements made in coincidence with dimer and trimer ions are used to effect an examination of the PECD associated with ionization of size-selected neutral cluster species, and these results differ clearly from PECD of the neutral monomer. The shifted ionization thresholds of the n-mers (n = 2, ..., 7) are shown to follow a simple linear relationship, but under intense beam expansion conditions the monomer deviates from this relationship, and the monomer electron spectra tail to below the expected monomer adiabatic ionization potential (IP). PECD measurements made in coincidence with monomer ions obtained under different beam expansion conditions were used to identify unambiguously a contribution from dissociative photoionization of larger clusters to the monomer parent mass ion yield above and below its adiabatic IP.

Coexistence of two donor packing motifs in the stable molecular metal α-‘pseudo-κ’-(BEDT-TTF)4(H3O)[Fe(C2O4)3]·C6H4Br2

The crystal and electronic structure of a new radical cation salt α-‘pseudo-κ’-(BEDT-TTF)4H3O[Fe(C2O4)3]·C6H4Br2 have been studied. The new triclinic crystals contain two conducting organic layers which are characterized by different BEDT-TTF packing motifs: a ‘pseudo-κ’-layer which is composed of charged dimers and neutral monomers of BEDT-TTF orthogonal to each other and an α-layer which consists of inclined, uniformly charged BEDT-TTF stacks. According to electronic band structure calculations, the ‘pseudo-κ’ layer has a large gap between the HOMO bands at the Fermi level and should be associated with an activated conductivity. In contrast, the α-layer is a strongly two-dimensional electronic system with uniform intermolecular interactions. The absence of any nesting in the Fermi surface of the α-layer suggests that this salt should be a stable metal down to low temperatures. Metallic properties have been observed in the crystals in the 300–0.4 K temperature range. Besides, well pronounced Shubnikov–de Haas oscillations of the magnetoresistance have been revealed at B > 8 T. The salt investigated is a new phase in the (BEDT-TTF)4AI[MIII(C2O4)3]G family of organic molecular conductors with paramagnetic anions and different guest solvent molecules G in the anion layer. Structural features of the new α-‘pseudo-κ’-crystals and other known phases of the family (β″, ‘pseudo-κ’ and α-β″) have been compared.

Synthetic hydrogels as scaffolds for manipulating endothelium cell behaviors

Synthetic hydrogels can be used as scaffolds that not only favor endothelial cells (ECs) proliferation but also manipulate the behaviors and functions of the ECs. In this review paper, the effect of chemical structure, Young’s modulus (E) and zeta potential (ζ) of synthetic hydrogel scaffolds on static cell behaviors, including cell morphology, proliferation, cytoskeleton structure and focal adhesion, and on dynamic cell behaviors, including migration velocity and morphology oscillation, as well as on EC function such as anti-platelet adhesion, are reported. It was found that negatively charged hydrogels, poly(2-acrylamido-2-methylpropanesulfonic sodium) (PNaAMPS) and poly(sodium p-styrene sulphonate) (PNaSS), can directly promote cell proliferation, with no need of surface modification by any cell-adhesive proteins or peptides at the environment of serum-containing medium. In addition, the Young’s modulus (E) and zeta potential (ζ) of hydrogel scaffolds are quantitatively tuned by copolymer hydrogels, poly(NaAMPS-co-DMAAm) and poly(NaSS-co-DMAAm), in which the two kinds of negatively charged monomers NaAMPS and NaSS are copolymerized with neutral monomer, N,N-dimethylacrylamide (DMAAm). It was found that the critical zeta potential of hydrogels manipulating EC morphology, proliferation, and motility is ζ critical = −20.83 mV and ζ critical = −14.0 mV for poly(NaAMPS-co-DMAAm) and poly(NaSS-co-DMAAm), respectively. The above mentioned EC behaviors well correlate with the adsorption of fibronectin, a kind of cell-adhesive protein, on the hydrogel surfaces. Furthermore, adhered platelets on the EC monolayers cultured on the hydrogel scaffolds obviously decreases with an increase of the Young’s modulus (E) of the hydrogels, especially when E > 60 kPa. Glycocalyx assay and gene expression of ECs demonstrate that the anti-platelet adhesion well correlates with the EC-specific glycocalyx. The above investigation suggests that understanding the relationship between physic-chemical properties of synthetic hydrogels and cell responses is essential to design optimal soft and wet scaffolds for tissue engineering.

Mechanistic Aspects of Radiation-Induced Oligomerization of 3,4-Ethylenedioxythiophene in Ionic Liquids

Thiophene and its disubstituted derivatives, such as 3,4-ethylenedioxythiophene (EDOT), 3,4-dimethoxythiophene (DMT), 3,4-propylenedioxythiophene (PDOT), and 3,4-butylenedioxythiophene (BuDOT) were oxidized in organic solvents and in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)PF₆⁻) at RT and under cryogenic conditions. Their radical cations were spectrally characterized at 77 K. Annealing of the irradiated matrix, which triggers the diffusion processes, led to spontaneous oligomerization. The oxidative coupling between a radical cation and a neutral monomer was identified as the first step of the oligomerization process. The scale of oligomerization could be extended by the addition of chloroform, which acts as a dissociative electron scavenger, whereas the dichloromethylperoxyl radicals formed in the reaction with the dissolved oxygen act as secondary oxidizing agents.

Synthesis, structure, spectroscopic properties, and theoretical studies of alkaline earth metal complexes of 1,3-bis(carboxymethyl)benzimidazolium

Alkaline earth metal complexes of 1,3-bis(carboxymethyl)benzimidazolium (HL) including [Mg(L) 2(H 2O) 4]·2H 2O ( 1), [Ca(L) 2(H 2O) 4]·2H 2O ( 2) and [Ba(L) 2(H 2O) 2·2H 2O] n ( 3) have been synthesized by a hydrothermal procedure and characterized by X-ray crystallography, spectroscopy and thermoanalysis. The results of X-ray crystallography revealed that complexes 1 and 2 are neutral monomers, while complex 3 is a polymeric species, and the carboxymethyl moiety of the deprotonated ligand (L −) acts as a bridge between metal ions. The spectroscopic properties of the complexes were evaluated through density functional theory (DFT) and time-dependent density functional theory (TD DFT) calculations. The results revealed that the absorption peaks in UV–Vis spectra were derived from ligand to ligand charge-transfer transitions (LLCT) and/or (p, π) → ( σ ∗, π ∗) intraligand charge-transfer (ILCT). HL and HL-based complexes displayed similar emission peaks in the near-UV region due to ligand-based LLCT. The results of the Fukui index of the complexes supported LLCT and ILCT mechanisms. In addition, the calculated value of the luminescence oscillator strength displayed a linear relationship with the charge distribution, and the DFT chemical reactivity index, and correlation coefficients ( R 2) of 0.999 and 0.996 were obtained, respectively. Thus, the results revealed that the emission strength of the complex can be controlled by coordinating the ligand to different metal ions.