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We demonstrate here how nitrate salts of bivalent copper, nickel, cobalt, and manganese, along with an achiral organic ligand, assemble into various structures such as symmetrical double‐decker flowers, smooth elongated hexagonal bipyramids, and hexagonal prisms. Large morphological changes occur in these structures because of different metal cations, although they maintain isomorphous hexagonal crystallographic structures. Metal cations with stronger coordination to ligands (Cu and Ni) tend to form uniform crystals with unusual shapes, whereas weaker coordinating metal cations (Mn and Co) produce crystals with more regular hexagonal morphologies. The unusual flower‐like crystals formed with copper nitrate have two pairs of six symmetrical petals with hexagonal convex centers. The texture of the petals indicates dendritic growth. Two different types of morphologies were formed by using different copper nitrate‐to‐ligand ratios. An excess of the metal salt results in uniform and hexagonal crystals having a narrow size distribution, whereas the use of an excess of ligand results in double‐decker morphologies. Mechanistically, an intermediate structure was observed with slightly concave facets and a domed center. Such structures most likely play a key role in the formation of double‐decker crystals that can be formed by fusion processes. The coordination chemistry results in isostructural chiral frameworks consisting of two types of continuous helical channels. Four pyridine units from four separate ligands are coordinated to the metal center in a plane having a chiral (propeller‐type) arrangement. The individual double‐decker flower crystals are homochiral and a batch consists of crystals having both handedness. [ABSTRACT FROM AUTHOR]

In this study, the precise positioning and alignment of arrays of two different guest molecules in a crystalline host matrix has been engineered and resulted in new optically active materials. Sub‐nm differences in the diameters of two types of 1D channels are sufficient for size‐selective inclusion of dyes. Energy transport occurs between the arrays of different dyes that are included in parallel‐positioned nanochannels by Förster resonance energy transfer (FRET). The color of individual micro‐sized crystals are dependent on their relative position under polarized light. This angular‐dependent behavior is a result of the geometrically constrained orientation of the dyes by the crystallographic packing of the host matrix and is concentration dependent. [ABSTRACT FROM AUTHOR]

Formation of highly interpenetrated frameworks is demonstrated. An interesting observation is the presence of very large adamantane‐shaped cages in a single network, making these crystals new entries in the collection of diamondoid‐type metal–organic frameworks (MOFs). The frameworks were constructed by assembling tetrahedral pyridine ligands and copper dichloride. Currently, the networks' degree of interpenetration is among the highest reported and increases when the size of the ligand is increased. Highly interpenetrated frameworks typically have low surface contact areas. In contrast, in our systems, the voids take up to 63 % of the unit cell volume. The MOFs have chiral features but are formed from achiral components. The chirality is manifested by the coordination chemistry around the metal center, the structure of the helicoidal channels, and the motifs of the individual networks. Channels of both handednesses are present within the unit cells. This phenomenon shapes the walls of the channels, which are composed of 10, 16, or 32 chains correlated with the degree of interpenetration 10‐, 16‐, and 32‐fold, respectively. By changing the distance between the center of the ligand and the coordination moieties, we succeeded in tuning the diameter of the channels. Relatively large channels were formed, having diameters up to 31.0 Å×14.8 Å. [ABSTRACT FROM AUTHOR]

We demonstrate high-performance electrochromic assemblies that exhibit a practical combination of low-voltage operation and efficient electrochromic switching as well as long-term thermal and redox stability (1.12 × 105 cycles). Our molecular assemblies can be integrated into a solid-state configuration. Furthermore, we also show how the molecular structure of the chromophores correlates with the materials' growth and function. The coloration efficiencies of our assemblies are higher than those of inorganic materials and many conducting polymers, in addition to offering an alternative fabrication approach. [ABSTRACT FROM AUTHOR]

We show that metal–organic frameworks, based on tetrahedral pyridyl ligands, can be used as a morphological and structural template to form a series of isostructural crystals having different metal ions and properties. An iterative crystal‐to‐crystal conversion has been demonstrated by consecutive cation exchanges. The primary manganese‐based crystals are characterized by an uncommon space group (P622). The packing includes chiral channels that can mediate the cation exchange, as indicated by energy‐dispersive X‐ray spectroscopy on microtome‐sectioned crystals. The observed cation exchange is in excellent agreement with the Irving–Williams series (MnZn) associated with the relative stability of the resulting coordination nodes. Furthermore, we demonstrate how the metal cation controls the optical and magnetic properties. The crystals maintain their morphology, allowing a quantitative comparison of their properties at both the ensemble and single‐crystal level. [ABSTRACT FROM AUTHOR]

We demonstrate here a unique metallo‐organic material where the appearance and the internal crystal structure are in contradiction. The egg‐shaped (ovoid) crystals have a brain‐like texture. Although these micro‐sized crystals are monodispersed; like fingerprints their grainy surfaces are never exactly alike. Remarkably, our X‐ray and electron diffraction studies unexpectedly revealed that these structures are single‐crystals comprising a continuous coordination network of two differently shaped homochiral channels. By using the same building blocks under different reaction conditions, a rare series of crystals have been obtained that are uniquely rounded in their shape. In stark contrast to the brain‐like crystals, these isostructural and monodispersed crystals have a comparatively smooth appearance. The sizes of these crystals vary by several orders of magnitude. [ABSTRACT FROM AUTHOR]

Abstract: We demonstrate the mediation of charge transport and release in thin films and devices by shifting the redox properties of layers of metal complexes by light. The nanoscale surface arrangement of both photo‐ and electrochemically‐active components is essential for the function of the thin films. Layers of well‐defined ruthenium complexes on indium‐tin‐oxide electrodes provide electron‐transport channels that allow the electrochemical addressing of layers of isostructural cobalt complexes. These cobalt complexes are electrochemically inactive when assembled directly on transparent metal‐oxide electrodes. The interlayer of ruthenium complexes on such electrodes allows irreversible oxidation of the cobalt complexes. However, shifting the redox properties of the ruthenium complexes by excitation with light opens up an electron‐transport channel to reduce the cobalt complexes; hence releasing the trapped positive charges. [ABSTRACT FROM AUTHOR]

In this study we have used a tetrahedral oligopyridine and four different fluoroiodides to obtain three-dimensional (3D) nanoporous halogen-bonded cocrystals. Many of the halogen-bonded cocrystals reported to date are one-dimensional chains or two-dimensional sheet-like structures; these new cocrystals possess multiple channels of 300-800 ų volume per unit cell. The extended 3D channels can be designed by varying the molecular structure of the halogen bond donor and were found to occupy 20-40% of the unit cell volume. The N···I distances in our cocrystals are ∼80% of the sum of the van der Waals radii of the nitrogen and iodine atoms, and the N···I-C angles are nearly linear. Noncovalent stacking (π-π) interactions as well as H-bonding to solvents were also observed in some of the cocrystals. The supramolecular structures obtained in this study are effectively derived out of different donor-acceptor XB interactions, solvent and other noncovalent interactions. The weak nature of halogen bonds as well as the existence of multiple interactions make these cocrystal structures and their supramolecular organization difficult to predict. Even though this work does not attempt to single out the individual contributions of different factors affecting the supramolecular assemblies, we show here how the structure and hence the potential porosity of the halogen-bonded organic frameworks can be varied via careful design and combination of structurally different donors and acceptors. [ABSTRACT FROM AUTHOR]

We report here a new methodology for the formation of freestanding nanotubes composed of individual gold nanoparticles (NPs) cross-linked by coordination complexes or porphyrin molecules using WS2 nanotubes (INT-WS2) as a template. Our method consists of three steps: (i) coverage of these robust inorganic materials with monodispersed and dense monolayers of gold NPs, (ii) formation of a molecular AuNP network by exposing these decorated tubes to solutions containing a ruthenium polypyridyl complex or meso-tetra(4-pyridyl)porphyrin, and (iii) removal of the INT-WS2 template with a hydrogen peroxide solution. Nanoindentation of the template-free AuNP tubes with atomic force microscopy indicates a radial elastic modulus of 4 GPa. The template-free molecular AuNP tubes are characterized using scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-Raman spectroscopy. The methodology provides a convenient and scalable strategy for the realization of molecular AuNP tubes with a defined length and diameter, depending on the dimensions of the template. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate a versatile approach for the formation of electrochromic nanoscale assemblies on transparent conductive oxides on both rigid and flexible substrates. Our method is based on the application of alternating spin-coated layers of well-defined metal polypyridyl complexes and a palladium(II) salt to form electrochemically addressable films with a high chromophore density. By varying the central metal ion of the polypyridyl complexes (Os, Ru, and Fe) and their ligands and by mixing these complexes, coatings with a wide range of colors can be achieved. These coatings cover a large area of RGB color space. The coloration intensities of these nanoscale films can be tuned by the number of deposition steps. The materials have very attractive ON/OFF ratios, electrochemical stabilities, and coloration efficiencies. Reversible color-to-colorless and color-to-color transitions were demonstrated, and the films were further integrated into sandwich cells. [ABSTRACT FROM AUTHOR]

Redox reactions play key roles in fundamental biological processes. The related spatial organization of donors and acceptors is assumed to undergo evolutionary optimization facilitating charge mobilization within the relevant biological context. Experimental information from submolecular functional sites is needed to understand the organization strategies and driving forces involved in the self-development of structure–function relationships. Here we exploit chemically resolved electrical measurements (CREM) to probe the atom-specific electrostatic potentials (ESPs) in artificial arrays of bacteriochlorophyll (BChl) derivatives that provide model systems for photoexcited (hot) electron donation and withdrawal. On the basis of computations we show that native BChl’s in the photosynthetic reaction center (RC) self-assemble at their ground-state as aligned gates for functional charge transfer. The combined computational and experimental results further reveal how site-specific polarizability perpendicular to the molecular plane enhances the hot-electron transport. Maximal transport efficiency is predicted for a specific, ∼5 Å, distance above the center of the metalized BChl, which is in remarkably close agreement with the distance and mutual orientation of corresponding native cofactors. These findings provide new metrics and guidelines for analysis of biological redox centers and for designing charge mobilizing machines such as artificial photosynthesis. [ABSTRACT FROM AUTHOR]

In this paper, we demonstrate how photochemically enhancing the permeability of metal-organic assemblies results in a significant enhancement of the electrochemical activity of metal complexes located within the assembly. The molecular assemblies consist of different layers of redox-active metal complexes ([M(mbpy-py)3][PF6]2; M = Ru or Os) that are separated by redox-inactive spacers consisting of 1,4-bis[2-(4-pyridyl)ethenyl]benzene (BPEB) and PdCl2 of variable thicknesses (0-13.4 nm). UV-irradiation (λ = 254 nm) of our assemblies induces a photochemical reaction in the redox-inactive spacer increasing the permeability of the assembly. The observed increase was evident by trapping organic (nBu4NBF4) and inorganic (NiCl2) salts inside the assemblies, and by evaluating the electrochemical response of quinones absorbed inside the molecular assemblies before and after UV irradiation. The increase in permeability is reflected by higher currents and a change in the directionality of electron transfer, i.e., from mono- to bidirectional, between the redox-active metal complexes and the electrode surface. The supramolecular structure of the assemblies dominates the overall electron transfer properties and overrules possible electron transfer mediated by the extensive π-conjugation of its individual organic components. [ABSTRACT FROM AUTHOR]

The article describes the selective optical detection and parts per million level quantification of Cr6+ in acidic water and MeCN using 1-based monolayers on float glass substrates. According to the authors, the redox processes with the surface-confined complex are fully reversible and can be monitored in the ex situ using standard ultraviolet/vis spectroscopy. The physicochemical properties and device performance of the 1-based monolayer are described.

We demonstrate a process that results in the formation of palladium nanoparticles during the assembly of molecular thin films. These nanoparticles are embedded in the films and are generated by a chemical reaction of the counter anions of the molecular components with the metal salt that is used for cross-linking these components. [ABSTRACT FROM AUTHOR]

The immobilization of metal nanoparticles (NPs) with molecular control over their organization is challenging. Herein, we report the formation of molecularly cross-linked AuNP assemblies using a layer-by-layer approach. We observed four types of assemblies: 1) small aggregates of individual AuNPs, 2) large aggregates of individual AuNPs, 3) networks of fused AuNPs, and 4) gold islands. Interestingly, these assemblies with the different cross-linkers and capping layers represent different stages in the complete fusion of AuNPs to afford islands of continuous gold. We demonstrate that the stability toward fusion of the nanoparticles of the on-surface structures can be controlled by the reactivity of the cross-linkers and the hydrophilicity/hydrophobicity of the nanoparticles. [ABSTRACT FROM AUTHOR]

The article presents a study on enhancement of molecular properties in thin films by controlled orientation of molecular building blocks. In this study researchers describe the design and formation of porphyrin-based thin films having divergent physical and chemical properties by using two molecular building blocks with high chemical and optical resemblance. Researchers made use of functionalized prophyrin because the poryphyrin's macrocycle has a rigid disklike shape with a large geometrical aspect ratio.

This contribution describes the reactivity of a zero-valent palladium phosphine complex with substrates that contain both an aryl halide moiety and an unsaturated carbon-carbon bond. Although η2-coordination of the metal center to a CC or CC unit is kinetically favored, aryl halide bond activation is favored thermodynamically. These quantitative transformations proceed under mild reaction conditions in solution or in the solid state. Kinetic measurements indicate that formation of η2-coordination complexes are not nonproductive side-equilibria, but observable (and in several cases even isolated) intermediates en route to aryl halide bond cleavage. At the same time, DFT calculations show that the reaction with palladium may proceed through a dissociation-oxidative addition mechanism rather than through a haptotropic intramolecular process (i.e., ring walking). Furthermore, the transition state involves coordination of a third phosphine to the palladium center, which is lost during the oxidative addition as the Chalide bond is being broken. Interestingly, selective activation of aryl halides has been demonstrated by adding reactive aryl halides to the η2-coordination complexes. The product distribution can be controlled by the concentration of the reactants and/or the presence of excess phosphine. [ABSTRACT FROM AUTHOR]

We demonstrate how the distance over which electron transfer occurs through organic materials can be controlled and extended. Coating of conductive surfaces with nanoscale layers of redox-active metal complexes allows the electrochemical addressing of distant layers that are otherwise electrochemically silent. Our materials can pass electrons selectively in directions that are determined by positioning of layers of metal complexes and the distances between them. These electron-transfer processes can be made dominantly uni- or bidirectional. The design involves 1) a set of isostructural metal complexes with different electron affinities, 2) a scalable metal-organic spacer, and 3) a versatile assembly approach that allows systematic variation of composition, structure, and electron-transfer properties. We control the electrochemical communication between interfaces by the deposition sequence and the spacer length, therefore we are able to program the bulk properties of the assemblies. [ABSTRACT FROM AUTHOR]

This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast η²-C C coordination of only one Pd(PEt3)2 moiety, which then significantly slows down the subsequent reaction. Electronic effects induced by complexation of the first metal center have a major effect on the subsequent formation of the bimetallic complexes. These effects are reduced by partial fluorination of the bis(vinylpyridine)-arene ligand. The monometallic complexes display migration of the Pd(PEt3)2 moiety between the two olefinic bonds of the corresponding ligand, as indicated by various solution NMR experiments, including variable-temperature NMR spectroscopy, 2D ¹H-¹H exchange spectroscopy, and spin saturation transfer. Density functional theory studies were performed at the SMD(toluene)-PBE0+d(v3)/B2//B97D/B1 level of theory. [ABSTRACT FROM AUTHOR]

Keywords: Cathodoluminescence; Fluorescence; Magnetic Properties; Metal Cation Metathesis; Metal-Organic Frameworks EN Cathodoluminescence Fluorescence Magnetic Properties Metal Cation Metathesis Metal-Organic Frameworks 1 1 1 08/19/22 20220822 NES 220822 B Predicting crystal morphologies b is challenging because of the many factors influencing their growth. Cathodoluminescence, Fluorescence, Magnetic Properties, Metal Cation Metathesis, Metal-Organic Frameworks Inside Back Cover: Directing the Morphology, Packing, and Properties of Chiral Metal-Organic Frameworks by Cation Exchange (Angew. [Extracted from the article]

Keywords: Cathodoluminescence; Fluorescence; Magnetic Properties; Metal Cation Metathesis; Metal-Organic Frameworks EN Cathodoluminescence Fluorescence Magnetic Properties Metal Cation Metathesis Metal-Organic Frameworks 1 1 1 08/18/22 20220822 NES 220822 B Die Vorhersage von Kristallmorphologien b ist aufgrund der vielen Faktoren, die das Kristallwachstum beeinflussen, eine Herausforderung. Cathodoluminescence, Fluorescence, Magnetic Properties, Metal Cation Metathesis, Metal-Organic Frameworks Die Tatsache, dass die Kristalle ihre Morphologie beibehalten, erleichtert einen quantitativen Vergleich ihrer optischen und magnetischen Eigenschaften. [Extracted from the article]

Here we show a step-wise approach for the formation of continuous shell-structures on surface-confined gold nanoparticles. The nanoparticle-cores induce order in the shell-structure, which consists of metal–organic networks. Communication between the organic and inorganic parts is reflected in their optical properties. [ABSTRACT FROM AUTHOR]

Surface-confined double-helical polymers are generated by dynamic covalent assembly with preservation of chirality, metal coordination environment, and oxidation state of the precursor complexes. This one-step procedure involves both in solution and solution-to-surface assembly and resulted in chiral interfaces where pairs of ligands are wrapped around arrays of metal ions. In-plane XRD experiments revealed the formation of a highly ordered structure along the substrate surface. The chirality of the surfaces is expressed by the selective recognition of 3,4-dihydroxyphenylalanine (DOPA). The CD measurements show a response of the Δ-polymer-modified quartz substrates toward d-DOPA, whereas no change was observed after treatment with L-DOPA. These coordination-based interfaces assembled on metal-oxide substrates in combination with a redox-probe, [Os(bpy)3](PF6)2, in solution can resemble the behavior of a rectifier. [ABSTRACT FROM AUTHOR]

The controlled deposition of metal complexes from solution on inorganic surfaces offers access to functional materials that otherwise would be elusive. For such surface-confined interfaces to form, specific assembly sequences are often used. We show here that varying the assembly sequence of two well-defined and iso-structural osmium and ruthenium polypyridyl complexes results in interfaces with strikingly different spectroelectrochemical properties. Successive deposition of redox-active layers of osmium and ruthenium polypyridyl complexes, leads to self-propagating molecular assemblies (SPMAs) with distinct internal interfaces and individually addressable components. In contrast, the clear separation of these interfaces upon sequential deposition of these two complexes, results in charge trapping or electrochemical communication between the metal centers, as a function of layer thickness and applied assembly sequence. The SPMAs were characterized using a variety of techniques, including: UV–vis spectroscopy, spectroscopic ellipsometry, electrochemistry, synchrotron X-ray reflectivity, angle-resolved X-ray photoelectron spectroscopy, and spectroelectrochemistry. The combined data demonstrate that the sequence-dependent assembly is a decisive factor that influences and provides the material properties that are difficult to obtain otherwise. [ABSTRACT FROM AUTHOR]

Molecular assemblies (MAs) of oligofurans and oligothiophenes were formed from solutions on various substrates. These films were obtained by alternating deposition of organic chromophores (oligofurans or oligothiophenes) and a palladium salt. These coordination-based MAs were characterized by UV/Vis spectroscopy, spectroscopic ellipsometry, atomic force microscopy (AFM), X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), and electrochemistry. The MAs exhibit similar electrochemical behavior and their growth and structure are apparently not affected when different organic template layers are used. The density of the MAs is a function of the structure of the molecular component. The oligothiophene density is approximately 50 % higher than that observed for the oligofuran-based assemblies. The optical and electrochemical properties of the MAs scale linearly with their thickness. The UV/Vis data indicate that upon increasing the film thickness, there is no significant conjugation between the metal-separated organic chromophores. DFT calculations confirmed that the HOMO-LUMO gap of the surface-bound oligofuran and oligothiophene metal oligomers do not change significantly upon increasing their chain length. However, electrochemical measurements indicate that the susceptibility of the MAs towards oxidation is dependent on the number of chromophore units. [ABSTRACT FROM AUTHOR]

Metal-organic networks (MONs) were created by a stepwise solution deposition approach from vinylpyridine-based building blocks and PdCl2. The combined experimental and computational study demonstrates the formation of saturated, structurally organized systems on solid supports. The rigid nature and geometry of the components are well-suited to form honeycomb and parallelogram structures, as predicted by a computational study. Detailed structural information of the new MONs was obtained by optical (UV/vis) spectroscopy, ellipsometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and synchrotron X-ray reflectivity (XRR). Notably, the XPS elemental composition indicates the formation of a palladium coordination-based network. [ABSTRACT FROM AUTHOR]

Four analogous platinum stilbene- and stilbazole-based complexes exhibit unusual long-range heteronuclear spin-spin coupling in solution. Single crystal analysis and NMR experiments show that the 19F, 31P, and 195Pt nuclei communicate over large distances (0.9-1.3 nm) through bond rather than through space. Spin-spin couplings between 195Pt and 19F over seven bonds and between 31P and 19F over eight bonds are observed with 7JPtF = 2.9 Hz and 8JPF = 11.8 Hz. Remarkably, a very large spin coupling between 195Pt and 19F over six bonds (6JptF = 40.1 Hz) is also observed in a structurally related pyridinium complex. Experimental and gNMR (version 5.0) simulated 19F(1H), 31P(1H), and 195Pt(1H) spectra of the complexes reveal a three-spin AMY system (A = 31P, M 31P, Y = 19F) or a five-spin AMY3 flanked by a four-spin AMXY or a six-spin AMXY3 system (X = 195Pt), respectively. Density functional theory calculations at the PBE0/SDD level of theory show a π-conjugated metal-ligand network, which may contribute to the experimentally observed spin-spin interactions. [ABSTRACT FROM AUTHOR]

Activation of a strong aryl-Br bond of a halogenated vinylarene by nickel(0) is demonstrated in the presence of aryl-I containing substrates. η²-Coordination of Ni(PEt3)2 to the CC moiety of halogenated vinylarenes is kinetically preferable and is followed by an intramolecular aryl-halide bond activation process. This `ring-walking" process is quantitative and proceeds under mild reaction conditions in solution. Mechanistic studies indicate that the metal insertion into the aryl-halide bond is not the rate-determining step. The reaction obeys first-order kinetics in the η²-coordination complexes with almost identical activation parameters for Br and I derivatives. The ring-walking process is kinetically accessible as shown by density functional theory (DFT) calculations at the PBE0/SDB-ccpVDZJ/PBE0/SDD level of theory. [ABSTRACT FROM AUTHOR]

The fluxional behavior of two analogous platinum complexes has been studied in solution by NMR spectroscopy to elucidate the reaction mechanism and to determine the activation parameters. This includes variable temperature NMR spectroscopy, 2D ¹H-¹H exchange spectroscopy, and spin saturation transfer measurements. A platinum moiety, Pt(PEt3)2, translocates between two carbon-carbon double bonds of two vinylpyridine moieties bridged by an arene (i.e., phenyl, anthracene) at elevated temperatures. Magnetization transfer NMR experiments in the presence of free ligands unambiguously revealed an intramolecular pathway for the "phenyl" system, An intermolecular pathway is proposed for the "anthracene" complex. [ABSTRACT FROM AUTHOR]

We demonstrated the one-pot disassembly of self-propagating molecular assemblies (SPMAs) by ligand exchange and the subsequent covalent binding of the molecular components to other surfaces. These functionalized surfaces are suitable for regenerating the SPMAs. [ABSTRACT FROM AUTHOR]

Halogen bonding between complementary organic monolayers was directly observed in an organic environment using force spectroscopy. This non-covalent interaction is significantly affected by the nature of the organic media. We also demonstrated the effect of lateral packing interactions on the optical properties of the monolayers. [ABSTRACT FROM AUTHOR]

This study provides insight into the internal structure of surface-confined molecular assemblies. The permeability of the layer-by-layer grown thin films can be controlled systematically by varying their composition and the structure of their molecular components. Moreover, the thickness can be used to control molecule permeation versus electron transfer. [ABSTRACT FROM AUTHOR]

Here we report the first use of self-propagating molecule-based assemblies (SPMAs) as efficient electron-transporting layers for inverted organic photovoltaic (OPV) cells. P3HT-PCBM cells functionalized with optimized SPMAs exhibit power conver- sion efficiencies approaching 3.6% (open circuit voltage = 0.6 V) vs 1.5% and 2.4% for the bare ITO and Cs2CO3-coated devices, respectively. The dependence of cell response parameters on interlayer thickness is investigated, providing insight into how to further optimize device performance. [ABSTRACT FROM AUTHOR]

Here we present the critical role of the molecular structure and reaction parameters on the nature of thin-film growth, using a versatile two-step assembly method with organic and metal-organic chromophores cross-linked with palladium. It was found that the polypyridyl complexes exhibit exponential growth, whereas, under identical conditions, the organic systems exhibit linear behavior. The internal film morphology plays a pivotal role in the storage and usage of the palladium, where a more porous structure results in exponential growth. Interestingly, through proper tuning of the reaction conditions, the growth of the molecular assemblies can be controlled, resulting in a changeover from exponential to linear growth. These findings unequivocally demonstrate the importance of both the internal film structure and deposition conditions on the assembly of molecular-based films. [ABSTRACT FROM AUTHOR]

The article focuses on the self-assembly of molecular-based multilayer that could yield functional organic lattices on a large variety of substrates which have been used for nanostructures, light emitting diodes, electro-optic modulators, and field effect transistors. It suggests that rich chemistry of surfaces engineered with molecular multilayers may be extended to important functions of polyelectrolyte-based films.

The article presents a study which discusses the approach for the preparation of highly effective electrochromic films through self-propagating molecular-based assembly. It showed that the combination of a redox-active and stable film can offer a useful entry to give new electrochromic materials, as well as the large variety of chromophores. Moreover, the study revealed that the charge-storage capability of the molecular-based assembly may make it an interesting candidate for battery.

The article reports on the assembly of crystalline halogen-bonded materials by physical vapor deposition (PVD). The authors report that the crystalline assemblies of 1 and 2, fabricated by PVD, exhibit controllable film morphologies. The authors state that halogen-bonded thin films may evolve into high quality functional materials.