Molecular Materials Research Articles

Formylation boosts the performance of light-driven overcrowded alkene-derived rotary molecular motors.

Artificial molecular motors and machines constitute a critical element in the transition from individual molecular motion to the creation of collective dynamic molecular systems and responsive materials. The design of artificial light-driven molecular motors operating with high efficiency and selectivity constitutes an ongoing fundamental challenge. Here we present a highly versatile synthetic approach based on Rieche formylation that boosts the quantum yield of the forward photoisomerization reaction while reaching near-perfect selectivity in the steps involved in the unidirectional rotary cycle and drastically reducing competing photoreactions. This motor is readily accessible in its enantiopure form and operates with nearly quantitative photoconversions. It can easily be functionalized further and outperforms its direct predecessor as a reconfigurable chiral dopant in cholesteric liquid crystal materials.

Alkali Metal–Substitution–Induced Confinement Effect for Designing High Phase–Transition–Temperature Molecular–Based Compounds Exhibiting Strong Photoluminescence

AbstractOrganic–inorganic hybrid phase–transition molecular materials have attracted increasing attention due to their excellent properties of combining inorganic and organic components. However, few research has been conducted on rare‐earth–based bimetallic organic–inorganic hybrids. Here, we successfully constructed a series of rare–earth–based organic–inorganic hybrid multifunctional materials, (C6H14N2)2EuX(NO3)6O2 (X=Na, K, Rb), with reversible phase transition, switchable dielectric, photoluminescence and semiconductor properties. Specifically, the phase‐transition temperature of three compounds are determined to be 364, 405 and 440 K, respectively. By the confinement effect caused by the variation of alkali metal elements in the two–dimensional structure, the phase transition temperature is successfully increased by 76 K. Meanwhile, the solid–state photoluminescence of three compounds displays bright red light at room temperature. Additionally, the bandgaps of three compounds are determined to be 3.21, 3.53 and 3.32 eV, respectively. It is expected that the strategy of alkali metal substitution proposed in this work will provide new thoughts for the design of multifunctional organic‐inorganic hybrid crystals.

Observing the Dynamics of an Electrochemically Driven Active Material with Liquid Electron Microscopy.

Electrochemical liquid electron microscopy has revolutionized our understanding of nanomaterial dynamics by allowing for direct observation of their electrochemical production. This technique, primarily applied to inorganic materials, is now being used to explore the self-assembly dynamics of active molecular materials. Our study examines these dynamics across various scales, from the nanoscale behavior of individual fibers to the micrometer-scale hierarchical evolution of fiber clusters. To isolate the influences of the electron beam and electrical potential on material behavior, we conducted thorough beam-sample interaction analyses. Our findings reveal that the dynamics of these active materials at the nanoscale are shaped by their proximity to the electrode and the applied electrical current. By integrating electron microscopy observations with reaction-diffusion simulations, we uncover that local structures and their formation history play a crucial role in determining assembly rates. This suggests that the emergence of nonequilibrium structures can locally accelerate further structural development, offering insights into the behavior of active materials under electrochemical conditions.

MesoHOPS: Size-invariant scaling calculations of multi-excitation open quantum systems.

The photoexcitation dynamics of molecular materials on the 10-100nm length scale depend on complex interactions between electronic and vibrational degrees of freedom, rendering exact calculations difficult or intractable. The adaptive Hierarchy of Pure States (adHOPS) is a formally exact method that leverages the locality imposed by interactions between thermal environments and electronic excitations to achieve size-invariant scaling calculations for single-excitation processes in systems described by a Frenkel-Holstein Hamiltonian. Here, we extend adHOPS to account for arbitrary couplings between thermal environments and vertical excitation energies, enabling formally exact, size-invariant calculations that involve multiple excitations or states with shared thermal environments. In addition, we introduce a low-temperature correction and an effective integration of the noise to reduce the computational expense of including ultrafast vibrational relaxation in Hierarchy of Pure States (HOPS) simulations. We present these advances in the latest version of the open-source MesoHOPS library and use MesoHOPS to characterize charge separation at a one-dimensional organic heterojunction when both the electron and hole are mobile.

Endowing Metal-Organic Coordination Materials with Chiroptical Activity by a Chiral Anion Strategy.

Recently, chiral metal-organic coordination materials have emerged as promising candidates for a wide range of applications in chiroptoelectronics, chiral catalysis, and information encryption, etc. Notably, the chiroptical effect of coordination chromophores makes them appealing for applications such as photodetectors, OLEDs, 3D displays, and bioimaging. The direct synthesis of chiral coordination materials using chiral organic ligands or complexes with metal-centered chirality is very often tedious and costly. In the case of ionic coordination materials, the combination of chiral anions with cationic, achiral coordination compounds through noncovalent interactions may endow molecular materials with desirable chiroptical properties. The use of such a simple chiral strategy has been proven effective in inducing promising circular dichroism and/or circularly polarized luminescence signals. This concept article mainly delves into the latest advances in exploring the efficacy of such a chiral anion strategy for transforming achiral coordination materials into chromophores with superb photo- or electro-chiroptical properties. In particular, ionic small-molecular metal complexes, metal clusters, coordination supramolecular assemblies, and metal-organic frameworks containing chiral anions are discussed. A perspective on the future opportunities on the preparation of chiroptical materials with the chiral anion strategy is also presented.

Series of Viologen-Based Metal-Organic Polyhedra with Photo/Electrochromic Behavior for Inkless Printing and UV Detection.

The fabrication of molecular crystalline materials with fast, multistimuli-responsive behavior and the construction of the corresponding structure-activity relationship are of extraordinary significance for the development of smart materials. In this context, three multistimuli-responsive functional metal-organic polyhedra (MOP), {[Dy2(bcbp)3(NO3)1.5(H2O)7]·Cl4.2·(NO3)0.3·H2O}n (1), {[Dy2(bcbp)4(H2O)8]Cl6}n (2), and {[Eu2(bcbp)4(H2O)10]Cl6·H2O}n (3; bcbp = 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium), were successfully prepared and characterized. All of the compounds exhibit rapid and reversible photochromic and electrochromic dual-responsive behaviors. Furthermore, benefiting from the well-defined crystal structure and different responsive behaviors, the photoinduced electron transfer (PIET) process and structure-activity relationship were explored. In addition, considering the excellent photochromic performance, function filter paper and smart organic glass were successfully prepared and used for ink-free printing and UV light detection.

On the Structural and Vibrational Properties of Solid Endohedral Metallofullerene Li@C60

The endohedral lithium fulleride, Li+@C60•−, is a potential precursor for new families of molecular superconducting and electronic materials beyond those accessible to date from C60 itself. Solid Li@C60 comprises (Li@C60)2 dimers, isostructural and isoelectronic with the (C59N)2 units found in solid azafullerene. Here, we investigate the structural and vibrational properties of Li@C60 samples synthesized by electrolytic reduction routes. The resulting materials are of high quality, with crystallinity far superior to that of their antecedents isolated by chemical reduction. They permit facile, unambiguous identification of both the reduced state of the fulleride units and the interball C-C bonds responsible for dimerization. However, severe orientational disorder conceals any crystal symmetry lowering due to the presence of dimers. Diffraction reveals the adoption of a hexagonal crystal structure (space group P63/mmc) at both low temperatures and high pressures, typically associated with close-packing of spherical monomer units. Such a situation is reminiscent of the structural behavior of the high-pressure Phase I of solid dihydrogen, H2.

Realization of Organocerium-Based Fullerene Molecular Materials Showing Mott Insulator-Type Behavior.

Electron-rich organocerium complexes (C5Me4H)3Ce and [(C5Me5)2Ce(ortho-oxa)], with redox potentials E1/2 = -0.82 V and E1/2 = -0.86 V versus Fc/Fc+, respectively, were reacted with fullerene (C60) in different stoichiometries to obtain molecular materials. Structurally characterized cocrystals: [(C5Me4H)3Ce]2·C60 (1) and [(C5Me5)2Ce(ortho-oxa)]3·C60 (2) of C60 with cerium-based, molecular rare earth precursors are reported for the first time. The extent of charge transfer in 1 and 2 was evaluated using a series of physical measurements: FT-IR, Raman, solid-state UV-vis-NIR spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and magnetic susceptibility measurements. The physical measurements indicate that 1 and 2 comprise the cerium(III) oxidation state, with formally neutral C60 as a cocrystal in both cases. Pressure-dependent periodic density functional theory calculations were performed to study the electronic structure of 1. Inclusion of a Hubbard-U parameter removes Ce f states from the Fermi level, opens up a band gap, and stabilizes FM/AFM magnetic solutions that are isoenergetic because of the large distances between the Ce(III) cations. The electronic structure of this strongly correlated Mott insulator-type system is reminiscent of the well-studied Ce2O3.

First-Principles Models of Polymorphism of Pharmaceuticals: Maximizing the Accuracy-to-Cost Ratio.

Accuracy and sophistication of in silico models of structure, internal dynamics, and cohesion of molecular materials at finite temperatures increase over time. Applicability limits of ab initio polymorph ranking that would be feasible at reasonable costs currently represent crystals of moderately sized molecules (less than 20 nonhydrogen atoms) and simple unit cells (containing rather only one symmetry-irreducible molecule). Extending the applicability range of the underlying first-principles methods to larger systems with a real-life significance, and enabling to perform such computations in a high-throughput regime represent additional challenges to be tackled in computational chemistry. This work presents a novel composite method that combines the computational efficiency of density-functional tight-binding (DFTB) methods with the accuracy of density-functional theory (DFT). Being rooted in the quasi-harmonic approximation, it uses a cheap method to perform all of the costly scans of how static and dynamic characteristics of the crystal vary with respect to its volume. Such data are subsequently corrected to agree with a higher-level model, which must be evaluated only at a single volume of the crystal. It thus enables predictions of structural, cohesive, and thermodynamic properties of complex molecular materials, such as pharmaceuticals or organic semiconductors, at a fraction of the original computational cost. As the composite model retains the solid physical background, it suffers from a minimum accuracy deterioration compared to the full treatment with the costly approach. The novel methodology is demonstrated to provide consistent results for the structural and thermodynamic properties of real-life molecular crystals and their polymorph ranking.

Bendable and Chemically Stable Metal-Organic Hybrid Membranes for Molecular Separation.

Crystalline porous metal-organic materials are ideal building blocks for separation membranes because of their molecular-sized pores and highly ordered pore structure. However, creating ultrathin, defect-free crystalline membranes is challenging due to inevitable grain boundaries. Herein, we reported an amorphous metal-organic hybrid (MOH) membrane with controlled microporosity. The synthesis of the MOH membrane entails the use of titanium alkoxide and organic linkers containing di/multicarboxyl groups as monomers in the polymerization reaction. The resultant membranes exhibit similar microporosity to existing molecular sieve materials and high chemical stability against harsh chemical environments owing to the formation of stable Ti-O bonds between metal centers and organic linkers. An interfacial polymerization is developed to fabricate an ultrathin MOH membrane (thickness of the membrane down to 80 nm), which exhibits excellent rejections (>98% for dyes with molecular weights larger than 690 Da) and high water permeance (55 L m-2 h-1 bar-1). The membranes also demonstrate good flexibility, which greatly improves the processability of the membrane materials.

Design and synthesis of a new family of the decanuclear Mn−Ln clusters: A novel approach to nonlinear optical molecular functional materials

For the first time, the {Mn5Ln5} (Ln = Sm (1), Eu (2), Gd (3), Dy (4) and Tb (5)) clusters were synthesized via a one-pot approach utilizing 2-amino-2-methyl-1.3-propanediol as the ligand. The clusters were well-characterized with Single-crystal X-ray diffraction, Powder X-ray diffraction and Fourier Transform Infrared spectra. Magnetic measurements revealed that the compounds 3 and 4 show weak ferromagnetic interactions. Besides, the {Mn5Sm5} film display prominent nonlinear optical performances with the large β of 1.28 × 10−7 m W−1, which indicates a great potential in optical limiting applications. Thus, the discovery of {Mn5Ln5} should open up new avenues for the design of NLO molecular functional materials by using 3 d and/or 4f metal cations.

Combining Molecular Motion with a 2,6-Diiodo BODIPY to Engineer Highly Anisotropic Thermomechanical Properties in Organic Binary and Ternary Molecular Materials

Combining Molecular Motion with a 2,6-Diiodo BODIPY to Engineer Highly Anisotropic Thermomechanical Properties in Organic Binary and Ternary Molecular Materials

Molecular and Supramolecular Materials: From Light-Harvesting to Quantum Information Science and Technology.

The past two decades have witnessed immense advances in quantum information technology (QIT), benefited by advances in physics, chemistry, biology, and materials science and engineering. It is intriguing to consider whether these diverse molecular and supramolecular structures and materials, partially inspired by quantum effects as observed in sophisticated biological systems such as light-harvesting complexes in photosynthesis and the magnetic compass of migratory birds, might play a role in future QIT. If so, how? Herein, we review materials and specify the relationship between structures and quantum properties, and we identify the challenges and limitations that have restricted the intersection of QIT and chemical materials. Examples are broken down into two categories: materials for quantum sensing where nonclassical function is observed on the molecular scale and systems where nonclassical phenomena are present due to intermolecular interactions. We discuss challenges for materials chemistry and make comparisons to related systems found in nature. We conclude that if chemical materials become relevant for QIT, they will enable quite new kinds of properties and functions.

A chiral metal–organic polyhedron used as stationary phase for gas chromatographic separations

Metal-organic polyhedra (MOPs), as a novel class of porous materials, exhibit distinctive application potential in molecular recognition, separation, catalysis, luminescent materials, drug delivery, and biomedicine owing to their tunable geometric shape and size, well-defined cavities, and discrete characteristics. In this study, we report that a chiral MOP [Cu12(LV)12(H2O)12] (V = L-valine) coated capillary column was used for gas chromatographic separations. The MOP coated capillary column offered the efficient separation of n-alkanes, alkylbenzenes, n-alcohols, multiple types of isomers, and enantiomers with high selectivity. Various enantiomers including esters, halogenated hydrocarbons, alcohols, ethers, aldehydes, and amino acid derivatives were well resolved on this chiral column, especially for some amino acid derivatives (e.g., Rs = 5.24 for tyrosine derivative). Compared with the commercial β-DEX 120 column for separation of the tested racemates, the chiral resolution performance of the MOP coated column can be complementary to that of β-DEX 120 column. Using 1,2-dichloropropane and o, m, p-dichlorobenzene as analytes, the MOP coated column exhibited good stability and reproducibility for gas chromatographic separations. The relative standard deviations (RSDs) of the retention time and peak area for repeated separation of 1, 2-dichloropropane and o, m, p-dichlorobenzene were less than 1.15 and 0.79 %, respectively. The results show that the chiral MOP holds great potential as a novel type of CSP for application in gas chromatography.

Interlocking viologen-based lanthanide complexes for multifunctionality: Photochromism, electrochromism, photoluminescence, photomagnetism, and inkless printing and UV shielding applications

The construction of molecular crystal materials with physical properties that can be dynamically controllable through various stimuli such as light and electricity is of extraordinary significance, while this remains a tremendous challenge. In this context, we demonstrate two novel 2-D multi-function viologen complexes, {[Ln(bcbp)(BDC)(CH3OH)(H2O)2]·Cl·CH3OH·H2O}n (1-Eu, and 2-Dy; H2bcbp·2Cl = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride; BDC = p-phthalic acid, and Ln = Eu, Dy). Due to the strong π-π interaction between viologen and BDC in the interlocked structure, both compounds exhibit rapid and reversible responses under the stimuli of UV light and electricity. Furthermore, accompanying the photochromic process, photo-modulated luminescent and photomagnetic behavior have been observed. Considering the excellent photochromic performance, the function filter paper and smart organic glass were successfully prepared and used for ink-free printing and UV light filtering.

Study on the Selectivity of Molecular Imprinting Materials Determined through Hydrogen Bonding on Template Molecular Structures of Flavonoids.

Molecular imprinting technology is widely used for the specific identification of compounds, but the selective recognition mechanisms of the same compounds still need to be further studied. Based on differences in hydrogen bond size and orientation, molecularly imprinted polymers (MIPs) were designed to adsorb flavonols with the same parent core and different hydroxyl groups. A surface-imprinted material was designed with silicon dioxide as the carrier, myricetin as the template molecule, and methacrylic acid (MAA) as the functional monomer. Scanning electron microscopy (SEM), Brunauer-Emmett-Teller surface area (BET) analyses, Fourier-transform infrared spectroscopy (FT-IR), and other characterization experiments were carried out. The intrinsic mechanism of the MIPs was also explored. The MIPs showed good adsorption of myricetin and other flavonoids through hydrogen bonding and steric hindrance. The adsorption capacity was 3.12-9.04 mg/g, and the imprinting factor was 1.78-3.37. Flavonoids with different hydroxyl groups in different numbers and directions had different hydrogen bond strengths with functional monomers. R2, R4, and R1 on 2-phenylchromogenone had stronger electronegativity, and the hydroxyl group was also more likely to form and have stronger hydrogen bonds. The hydroxyl negativity and the degree of steric hindrance of flavonoids played a major role in the recognition of molecularly imprinted materials. This study is of great significance for the synthesis of and selection of templates for analogous molecular imprinting materials.

C3-Symmetric Luminescent Diketone with Amido-Linkage as a Polymorphic Fluorescence Emitter.

The study introduces a novel C3-symmetric β-diketone compound, BTA-D3, and its monomeric counterpart, D, with a focus on their synthetic procedure, photophysical properties and aggregation behavior. Both compounds exhibit characteristic absorption and weak fluorescence in solution, with BTA-D3 displaying higher absorption coefficients due to its larger number of diketone units. Density Functional Theory (DFT) calculations suggest increased co-planarity of diketone groups in BTA-D3. A significant finding is the Aggregation-Induced Emission (AIE) property of BTA-D3, as its fluorescence intensity increases dramatically when exposed to specific solvent ratios. The AIE behavior is attributed to intermolecular excitonic interaction between BTA-D3 molecules in self-organized aggregates. We also studied fluorescence anisotropy of BTA-D3 and D. Despite its larger size, BTA-D3 showed reduced anisotropy values because of efficient intramolecular energy migration among three diketone units. Furthermore, BTA-D3 demonstrates unique polymorphism, yielding different emission colors and structures depending on the solvent used. A unique approach is presented for promoting the growth of self-organized aggregate structures via solvent evaporation, leading to distinct fluorescence properties. This research contributes to the understanding of C3-symmetric structural molecules and provides insights into strategies for controlling molecular alignment to achieve diverse fluorescence coloration in molecular materials.

Boron Complexes of Tridentate Acyl Pyridylhydrazones

AbstractSince the development of the chemistry and applications of boron dipyrromethene dyes (BODIPYs), numerous other platforms based on boron complexes of N‐donor ligands have emerged as molecular optoelectronic materials. By tailoring the structure of the ligand bound to boron, the optical and electronic properties of a compound can be precisely tuned for unique properties, such as aggregation‐induced emission (AIE) in the case of boron difluoride hydrazones (BODIHYs). We examine the impact of modifying the typical bidentate hydrazone ligand structure used to prepare BODIHYs to enable a tridentate coordination mode to produce boron complexes of tridentate acyl pyridylhydrazones. This change allows for the use of arylboronic acids as sources of boron and facilitates the inclusion of complex organic components at the boron centre, including the formation of dye‐dye conjugates. The synthesized compounds exhibit distinct optical and electronic properties when compared to BODIHYs, such as reversible electrochemical reduction and up to a >300 nm pseudo‐Stokes shift in the solid state, all of which were supported by density functional theory calculations.

Microbial exopolysaccharide composites with inorganic materials and their biomedical applications: A review

Microbial exopolysaccharides (EPS) are high molecular weight carbohydrate-based materials produced and secreted in response to external environmental stress to protect microbial cells. These molecules also contain non-carbohydrate moieties including acetate, pyruvate, phosphate, and succinate along with sugar molecules. EPS has been incorporated into industrial operations as a gelling, emulsifying, and stabilizing agent to increase viscosity. Besides, these molecules have also shown high biocompatibility, immunomodulatory, antitumor, anti-microbial, and anti-viral activity which suggest their possible applications in healthcare. However, these molecules are facing some commercial shortcomings due to low stability, bioactivity, and poor mechanical and tensile strength in comparison to the required standard. Hence use of composites of EPS with other polymers and moieties has been suggested for higher performance. Especially in the context of inorganic moieties like silver, gold nanomaterials, clay, salts, and minerals will add bioactivity and functional sites for the attachment of drug molecules and other compounds. The current review summarizes the higher physical and chemical characteristics of EPS composites with inorganic materials and their immense potential in the biomedical sector.

Unique Viscoelasticity and Hierarchical Relaxation Dynamics of Molecular Granular Materials.

Resulting from the dense packing of subnanometer molecular clusters, molecular granular materials (MGMs) are shown to maintain high elasticity far above their apparent glass transition temperature (Tg*). However, our microscopic understanding of their structure-property relationship is still poor. Herein, 1 nm polyhedral oligomeric silsesquioxanes (POSSs) are appended to a backbone chain in a brush configuration with different flexible linker chains. Assemblies of these brush polymers exhibit hierarchical relaxation dynamics with the glass transition arising from the cooperative dynamics of packed POSSs. The interaction among the assemblies can be strengthened by increasing the rigidity of linkers with the MGM relaxation modes changing from colloid- to polymer chain-like behavior, rendering their tunable viscoelasticity. This finally contributes to the decoupling of mechanical and thermal properties by showing elasticity dominant mechanical properties at a temperature 150 K above the Tg*.