Dimerization of Fe(III) Ion in an Aqueous Medium: Mechanistic Modelling and Effects of Ligands.

Aqueous iron solutions generally undergo spontaneous hydrolysis followed by aggregation resulting in the precipitation of nanocrystalline oxyhydroxide minerals. The mechanism of nucleation of such multinuclear oxyhydroxide clusters are unclear due to limited experimental evidence.  Here, we investigate the mechanistic pathway of dimerization of Fe(III) ions using density functional theory (DFT) in aqueous medium considering effects of other ligands. Two hydrolyzed monomeric Fe(III) ions in aqueous medium may react to form two closely related binuclear products, the m-oxo and the dihydroxo Fe2  dimer. Our studies indicate that the water molecules in the second coordination sphere and those co-ordinated to the Fe(III) ion, both participate in the dimerization process. The proposed mechanism effectively explains the formation of dihydroxo and µ-oxo Fe2 dimers with interconversion possibilities, for the first time. Results show, with only water molecules present in the second co-ordination sphere, dihydroxo Fe2 dimer is the thermodynamically and kinetically favored product with a low activation free energy. We calculated the step-wise reaction free energies of dimerization in the presence of nitrate ions in the first and second coordination sphere of Fe(III) ion separately, which shows that with nitrate ions in the second co-ordination sphere, the µ-oxo Fe2 dimer formation is kinetically favored.

Structural Rearrangement Followed by Entrapment of Subnanometer Building Blocks of Iron Oxyhydroxide in Aqueous Iron Chloride Solutions.

Iron oxyhydroxide, a natural nanophase of iron found in the environment, plays a crucial role in regulating surface and groundwater composition. Recent research proposes that within the nonclassical prenucleation cluster growth model, subnanometer-sized clusters (olation clusters/Fe13 δ-Keggin oxolation clusters) might act as the prenucleation clusters (PNCs) of ferrihydrite or iron oxyhydroxide solid phase. However, these clusters are difficult to characterize as they are only observable momentarily in low-pH, high-Fe concentration solutions before agglomerating into extended solids, keeping the controversy over the true nature of the PNCs alive. In this study, we introduce large quantities of zinc acetate salt (ZA) into iron chloride solutions at the olation-oxolation boundary (3.6 mM Fe3+ at pH ∼2.6). Remarkably, this manipulation is found to alter the structural arrangement of these subnanometer clusters before blocking them in isolation for hours, even at pH 6, where extended iron oxyhydroxide phases typically precipitate. On the other hand, controlled addition of ZA allows partial unblocking, leading to anisotropic agglomeration into cylindrical rod-like structures. Experimental techniques such as synchrotron-based small-angle X-ray scattering, X-ray absorption spectroscopy, high-resolution transmission electron microscopy (TEM), and cryo-TEM, along with density functional theory (DFT) calculations, reveal the nature of the structural rearrangement and the crucial role of Zn2+ ions in cluster stabilization.

Curious Behavior of Fe3+-As3+ Chemical Interactions and Nucleation of Clusters in Aqueous Medium.

The simultaneous presence of Fe3+ and As3+ ions in groundwater (higher ppb or lower ppm level concentrations at circumneutral pH) as well as in acid mine drainages (AMDs)/industrial wastewater (up to few thousand ppm concentration at strongly acidic pH) are quite common. Therefore, understanding the chemical interactions prevalent between Fe3+ and As3+ ions in aqueous medium leading to nucleation of ionic clusters/solids, followed by aggregation and growth, is of great environmental significance. In the present work, we attempt to probe the nucleation process of Fe3+-As3+ clusters in solutions of various concentrations and pHs (from AMD to groundwater-like) using a combination of experimental and theoretical techniques. Interestingly, our study reveals nucleation of primary FeAs clusters in nearly all of them independent of concentration or pH. Theoretical studies employed density functional theory (DFT) to predict the primary clusters as stable Fe4As4 units. The surprising resemblance of these clusters with known Fe3+-As3+ minerals at the local level was observed experimentally, which provides an important clue about solid-phase growth from a range of Fe3+-As3+ solutions. Our experimental findings are further supported by a stepwise reaction mechanism established from detailed DFT studies.

Mitigating Dendrite Formation on a Zn Electrode in Aqueous Zinc Chloride by the Competitive Surface Chemistry of an Imidazole Additive.

Electrochemical energy storage systems are critical in several ways for a smooth transition from nonrenewable to renewable energy sources. Zn-based batteries are one of the promising alternatives to the existing state-of-the-art Li-ion battery technology, since Li-ion batteries pose significant drawbacks in terms of safety and cost-effectiveness. Zn (with a reduction potential of -0.76 V vs SHE) has a significantly higher theoretical volumetric capacity (5851 mAh/cm3) than Li (2061 mAh/cm3), and it is certainly far less expensive, safer, and more earth-abundant. The formation of dendrites, hydrogen evolution, and the formation of a ZnO passivation layer on the Zn anode are the primary challenges in the development and deployment of rechargeable zinc batteries. In this work, we examine the role of imidazole as an electrolyte additive in 2 M ZnCl2 to prevent dendrite formation during zinc electrodeposition via experimental (kinetics and imaging) and theoretical density functional theory (DFT) studies. To characterize the efficacy and to identify the appropriate concentration of imidazole, linear sweep voltammetry (LSV) and chronoamperometry (CA) are performed with in situ monitoring of the electrodeposited zinc. The addition of 0.025 wt % imidazole to 2 M ZnCl2 increases the cycle life of Zn-symmetric cells cycled at 1 mA/cm2 for 60 min of plating and stripping dramatically from 90 to 240 h. A higher value of the nucleation overpotential is noted in the presence of imidazole, which suggests that imidazole is adsorbed at a competitively faster rate on the surface of zinc, thereby suppressing the zinc electrodeposition kinetics and the formation. X-ray tomography reveals that a short circuit caused by dendrite formation is the main plausible failure mechanism of Zn symmetric cells. It is observed that the electrodeposition of zinc is more homogeneous in the presence of imidazole, and its presence in the electrolyte also inhibits the production of a passivating coating (ZnO) on the Zn surface, thereby preventing corrosion. DFT calculations conform well with the stated experimental observations.

Binding of As3+ and As5+ to Fe(III) Oxyhydroxide Clusters and the Influence of Aluminum Substitution: A Molecular Perspective.

Fe(III) oxides and oxyhydroxides play a very important role in contaminant cycling and mobility in the environment through numerous sorption mechanisms owing to their nanoparticulate nature. Generally coprecipitated from mixtures of metal ions in natural environments, Fe(III) oxyhydroxides are often doped by various impurity metal ions to a certain degree. These dopant/impurity ions then play a crucial role in the geochemical cycling of toxic contaminants like arsenic via modified adsorption energetics on Fe(III) oxyhydroxide nanoparticles. Aluminum (Al) commonly coexists with ferric salts and minerals in nature and affects the arsenic (As) binding abilities of Fe(III) oxyhydroxides. We use electronic structure studies to model the As binding potential of Al-doped Fe(III) oxyhydroxide clusters, using a "bottom-up" molecular approach to understand their role in As fixation. We start from small Al-doped Fe(III) oxyhydroxide clusters, like dimers and trimers, and gradually study larger clusters including the δ-Fe13 Keggin cluster, evaluating their As binding potential with respect to pure undoped Fe(III) oxyhydroxide clusters at each step. The calculated reaction free energies clearly show that Al doping into Fe(III) oxyhydroxide clusters reduces their As3+ binding potential, whereas the As5+ binding is not affected much due to Al doping.

Origin of Intense Luminescence from Supramolecular 2D Molecular Crystals.

Luminescence enhancement in 2D molecular crystals (2D crystals) is promising for a variety of optical applications, yet the availability is limited because of unclear mechanism and inefficient design strategy of luminescence control. Herein, the room temperature phosphorescence from micron long molecular thin free-standing 2D crystals of a mono-cyclometalated Ir(III) complex designed at the water surface is reported. A large luminescence enhancement is observed from the 2D crystals at 300 K, which is comparable with the rigidified solution at 77 K suggesting room temperature phosphorescence origin of the luminescence. In situ synchrotron grazing incidence X-ray diffraction measurements determine the constituent centered rectangular unit cells with precise molecular conformation that promotes the formation of 2D crystals. The molecular crystal design leads to a reduced singlet-triplet energy gap (ΔEST ) and mixing of singlet-triplet states by spin-orbit coupling (SOC) for efficient intersystem crossing, which explains the phosphorescence origin at room temperature and luminescence enhancement. The supramolecular assembly process provides an elegant design strategy to realize room temperature phosphorescence from 2D crystals by rigid intermolecular interactions.

Electronic structure and transport properties of coupled CdS/ZnSe quantum dots.

Electronic structure and transport characteristics of coupled CdS and ZnSe quantum dots are studied using density functional theory and non equilibrium Greens function method respectively. Our investigations show that in these novel coupled dots, the Frontier occupied and unoccupied molecular orbitals are spatially located in two different parts, thereby indicating the possibility of asymmetry in electronic transport. We have calculated electronic transport through the coupled quantum dot by varying the coupling strength between the individual quantum dots in the limits of weak and strong coupling. Calculations reveal asymmetric current vs voltage curves in both the limits indicating the rectifying properties of the coupled quantum dots. Additionally we discuss the possibility to tune the switching behavior of the coupled dots by different gate geometries.

An insight into the catalytic activity of palladium Schiff-base complexes towards the Heck coupling reaction: routes via encapsulation in zeolite-Y.

A small set of palladium Schiff-base complexes were synthesized and entrapped in the supercage of zeolite-Y. All these novel complexes in both states were systematically characterized with the help of different characterization tools like XRD, SEM-EDS, thermal analysis, XPS, IR, electronic spectroscopic and theoretical studies. These systems were thoroughly studied for their catalytic activities towards the Heck coupling reaction between bromobenzene and styrene. The aim was to meticulously compare the performance of the homogeneous catalysts, i.e., neat palladium Schiff-base complexes with that of their heterogeneous encapsulated analogs. The experimental as well as theoretical electronic structure studies suggested significant structural modification of the guest Pd(ii)-Schiff-base complexes after encapsulation in zeolite Y. These complexes manifested modified catalytic activities towards the Heck coupling reaction. The theoretical studies reinforced the correlation between the modified catalytic properties and structural alteration of these complexes on encapsulation. These heterogeneous catalysts essentially demonstrated the benefits of easy separation and reusability as compared to the homogeneous analogues.

Zn(ii)-based coordination polymer: An emissive signaling platform for the recognition of an explosive and a pesticide in an aqueous system.

A new emissive Zn(ii)-based coordination polymer (Zn-CP) bearing paddle-wheel clusters has been developed and the same has been demonstrated to have potential for recognising a nitroaromatic-based explosive (TNP) and a pesticide (2,6-DCNA) in aqueous solution. The structural integrity of this newly developed 2D material was established through single-crystal analysis, whereas the stability of Zn-CP in aqueous medium after the recognition process was investigated by the powder-XRD technique. A combination of experimental and theoretical studies revealed that the change in fluorescence intensity of Zn-CP while interacting with TNP and 2,6-DCNA was possibly due to simultaneous operation of PET and FRET. Experimentally, it was also established that Zn-CP can be reused in up to three cycles for the detection of TNP and 2,6-DCNA.

Postsynthesis Spontaneous Coalescence of Mixed-Halide Perovskite Nanocubes into Phase-Stable Single-Crystalline Uniform Luminescent Nanowires.

All inorganic mixed-halide perovskite, CsPb(Br xI1- x)3 (0 ≤ x ≤ 1), nanocrystals possess tunable photoluminescence with high quantum yield in the visible window. However, the photoluminescence degrades rapidly with postsynthetic aging due to the spontaneous ion separation and phase instability. Here we show that the postsynthetic aging of CsPb(Br xI1- x)3 nanocubes spontaneously forms highly uniform single-crystalline nanowires with a diameter of 9 ± 0.5 nm and length of up to several micrometers. The nanowires show bright photoluminescence with an absolute photoluminescence quantum yield of 41%. Rietveld refinement identifies the stable orthorhombic phase of the nanowires, implying a phase transition from the cubic crystallographic phase of the nanocubes during the morphology evolution. Transient absorption spectroscopy reveals a faster excited-state decay dynamic with a large exciton delocalization length in 1D nanowires. Our findings elucidate the insights into the postsynthesis morphology evolution of mixed-halide perovskite nanocrystals leading to luminescent nanowires with excellent crystal phase stability for potential optoelectronic applications.

Palladium-Schiff Base Complexes Encapsulated in Zeolite-Y Host: Functionality Controlled by the Structure of a Guest Complex.

A series of palladium complexes of tetradendate Schiff base ligands L1 ( N,N'-bis(salicylidene)phenylene-1,3-diamine) and its derivatives L2 and L3 have been synthesized by using the "flexible ligand method" within the supercage of zeolite-Y. These complexes in both their free and encapsulated states have been thoroughly characterized with the help of different characterization tools such as XRD, SEM-EDS, BET, thermal analysis, XPS, IR, and UV-vis spectroscopic studies. All these encapsulated complexes are identified with a dramatic red shift of the d-d transition in their electronic spectra when compared with their free states. Theoretical as well as experimental studies together suggest a substantial modification of the structural parameters of square planar Pd(II)-Schiff base complexes upon encapsulation within the supercage of zeolite-Y. Encapsulated complexes are also subject to show modified catalytic activities toward the Heck reaction. These heterogeneous catalysts can easily be separated from the reaction mixture and reused.

Unidirectional Branching Growth of Dipeptide Single Crystals for Remote Light Multiplication and Collection.

Herein, we report on the unidirectional branched assembly of diphenylalanine dipeptide through a one-step rapid evaporation process. Large numbers of crystalline tubular branches with smooth surfaces are developed from a hexagonal solid microrod mimicking a "Christmas tree". Density functional theory suggests the formation of tubular diphenylalanine aggregates with cis isomers. The diphenylalanine branched assembly shows good optical waveguide properties that can transmit light homogeneously along the crystal fibers as well as harvest light from the tips of branches to the microrod terminals. These findings hold importance in the development of bioinspired optical fibers for information transmission in a microscale.

Supramolecular Aggregates of Tetraphenylethene-Cored AIEgen toward Mechanoluminescent and Electroluminescent Devices.

Luminescent materials possessing both the mechanoluminescence (MCL) and electroluminescence (EL) properties are the quest for sensing and optoelectronic applications. We report on the synthesis of a new tailor-made luminogen, 1,2-bis(4-(1-([1,1'-biphenyl]-4-yl)-2,2-diphenylvinyl)phenyl)-1,2-diphenylethene (TPE 5), using Suzuki coupling reaction with high yield. An aggregation-induced emission (AIE) active complex TPE 5 forms supramolecular spherical aggregates at the air-water interface of a Langmuir trough. As a consequence, a large enhancement of luminescence is obtained from the mono- and multilayer Langmuir-Blodgett films of TPE 5 owing to the AIE effect. The luminogen TPE 5 exhibits a reversible MCL response, displaying photoluminescence switching due to change in the crystalline states under external stimuli. The unique feature of luminescence enhancement upon aggregate formation is utilized for the fabrication of light-emitting diodes with low threshold voltage using supramolecular aggregates as the active layer. This work demonstrates an efficient strategy for obtaining controlled supramolecular aggregates of AIEgen with a potential in the dual applications of MCL and EL.

Theoretical Study of Small Iron-Oxyhydroxide Clusters and Formation of Ferrihydrite.

Hydrolysis of iron compounds in water leads to the formation of Fe(III) oyxhydroxide-based minerals like ferrihydrite, which act as natural scavengers of inorganic contaminants in the environment. Though studied widely, experimental identification of these oxyhydroxides remains very difficult due to their extreme reactivity. The present study theoretically investigates the formation of Fe(III) oxyhydroxides starting from a single hydrated Fe(III) ion, modeling the formation of larger clusters gradually. The structures, formation enthalpies, and free energies of dimers, trimers, tetramers, and even larger Fe(III) oxyhydroxide clusters comprising of Fe5, Fe7, and Fe13-Keggin ions in gaseous phase and in aqueous medium (using self-consistent reaction field method) are systematically studied using density functional theory. Spontaneous formation of certain multinuclear Fe(III) oxyhydroxide clusters with clear structural signatures of ferrihydrite highlights their potential as prenucleation clusters in the course of mineralization.

Induced Aggregation of AIE-Active Mono-Cyclometalated Ir(III) Complex into Supramolecular Branched Wires for Light-Emitting Diodes.

Aggregation-induced emission (AIE) is commonly observed in irregular bulk form. Herein, unique aggregation properties of an AIE-active complex into branched supramolecular wires are reported for the first time. Mono-cyclometalated Ir(III) complex shows in-plane J-aggregation at the air-water interface owing to the restriction of intramolecular vibration of bidentate phenylpyridinato and intramolecular rotations of monodentate triphenylphosphine ligands at air-water interface. As a consequence, a large enhancement of luminescence comparable to the solid state is obtained from the monolayers of supramolecular wires. This unique feature is utilized for the fabrication of light-emitting diodes with low threshold voltage using supramolecular wires as active layer. This study opens up the need of ordered assembly of AIE complexes to achieve optimal luminescence characteristics.

Enhanced catalytic activity and magnetization of encapsulated nickel Schiff-base complexes in zeolite-Y: a correlation with the adopted non-planar geometry.

Square planar Ni(ii)-Schiff base complexes when encapsulated in a supercage of zeolite Y have shown altered optical, magnetic properties and catalytic activities in comparison to their corresponding free states. Different characterization techniques like XRD analysis, SEM-EDX, AAS, FTIR, UV-Visible spectroscopy and magnetic studies as well as detailed theoretical studies altogether show the differences in the properties of complexes in free and encapsulated states. All these studies have suggested that the largest complex deviates by the maximum amount from its free-state properties and a fascinating correlation between the extent of deviation from molecular dimension and modified catalytic activity of encapsulated complexes is observed.

Efficient artificial mineralization route to decontaminate Arsenic(III) polluted water - the Tooeleite Way.

Increasing exposure to arsenic (As) contaminated ground water is a great threat to humanity. Suitable technology for As immobilization and removal from water, especially for As(III) than As(V), is not available yet. However, it is known that As(III) is more toxic than As(V) and most groundwater aquifers, particularly the Gangetic basin in India, is alarmingly contaminated with it. In search of a viable solution here, we took a cue from the natural mineralization of Tooeleite, a mineral containing Fe(III) and As(III)ions, grown under acidic condition, in presence of SO4(2-) ions. Complying to this natural process, we could grow and separate Tooeleite-like templates from Fe(III) and As(III) containing water at overall circumneutral pH and in absence of SO4(2-) ions by using highly polar Zn-only ends of wurtzite ZnS nanorods as insoluble nano-acidic-surfaces. The central idea here is to exploit these insoluble nano-acidic-surfaces (called as INAS in the manuscript) as nucleation centres for Tooeleite growth while keeping the overall pH of the aqueous media neutral. Therefore, we propose a novel method of artificial mineralization of As(III) by mimicking a natural process at nanoscale.

'All-Metal' Aromatic Sandwich Molecules: An Electronic Structure and Transport Study.

Electronic structure and transport is theoretically studied for neutral, all-metal aromatic sandwich molecules, Al4MAl4 (M = Cr, Mo) along with Al4 and Al4M (M = Cr, Mo) clusters in two-probe setups with silver and gold electrodes. Detailed electronic structure and transport studies of metallaromatic Al4MAl4 molecules show high electronic conductance [2.5*10(-4) S for Al4CrAl4 and 2.9*10(-4) S for Al4MoAl4] and three conduction channels simultaneously contribute to the total transmission probability. The study of transport properties of the bare Al4 cluster and Al4M cluster also show very high electronic conductance. The neutral Al4 cluster, when connected parallel to the electrodes, four Al atoms couple to the electrode atoms and at least eight electron conduction pathways contribute simultaneously to the conductance whereas for perpendicular connectivity only three conduction channels operate. All the molecules couple strongly to the electrodes by well-defined metal-metal bonds owing to their metallic nature indicating an easier electrode integration process, and the calculated current voltage curves are almost linear till applied voltages of 1 V for Al4MAl4 (M = Cr, Mo). The electronic transport of the clusters studied here resembles the values found for metal atomic chains in break junction studies.

Encapsulation of a Ni salen complex in zeolite Y: an experimental and DFT study.

It is observed that for a square planar Ni(II)-Schiff base complex of the general formula {Ni(II)L}, where L is {L: N,N'-bis(5-hydroxy-salicylidene)ethylenediamine}, when encapsulated in a supercage of zeolite Y the bulky guest complex adopts a non-planar geometry without disturbing the integrity of the zeolite framework. Detailed comparative characterization is carried out to understand the structural change of the guest complex as a result of steric and electronic interactions with the host framework. UV-Vis spectroscopic studies of the encapsulated and 'neat' complex show a significant blue shift in the d-d transition after encapsulation and the diamagnetic 'neat' complex exhibits paramagnetism after encapsulation. DFT studies of the Ni(II)-Schiff base complex have been carried out for different spin states in neat and encapsulated form and the UV-Vis spectra are simulated using TD-DFT to understand the observed spectra in detail.

Aligned 1-D nanorods of a π-gelator exhibit molecular orientation and excitation energy transport different from entangled fiber networks.

Linear π-gelators self-assemble into entangled fibers in which the molecules are arranged perpendicular to the fiber long axis. However, orientation of gelator molecules in a direction parallel to the long axes of the one-dimensional (1-D) structures remains challenging. Herein we demonstrate that, at the air-water interface, an oligo(p-phenylenevinylene)-derived π-gelator forms aligned nanorods of 340 ± 120 nm length and 34 ± 5 nm width, in which the gelator molecules are reoriented parallel to the long axis of the rods. The orientation change of the molecules results in distinct excited-state properties upon local photoexcitation, as evidenced by near-field scanning optical microscopy. A detailed understanding of the mechanism by which excitation energy migrates through these 1-D molecular assemblies might help in the design of supramolecular structures with improved charge-transport properties.