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A tellurorosamine dye [Te(II)] undergoes aerobic photooxidation. Although Te(IV) species have been used in a number of oxidations, key Te(IV)-oxo and Te(IV)-bis(hydroxy) intermediates are challenging to study. Under aerobic irradiation with visible light, Te(II) (λmax = 600 nm) transforms into a Te(IV) species (λmax = 669 nm). The resultant Te(IV) species is not stable in the dark or at -20 °C, decomposing back to Te(II) and other byproducts over many hours. To eliminate the structural ambiguity of the Te(IV) photoproduct, we used spectroelectrochemistry, wherein the bis(hydroxy) Te(IV)-(OH)2 was electrochemically generated under anaerobic conditions. The absorption of Te(IV)-(OH)2 matches that of the Te(IV) photoproduct. Because isosbestic points are maintained both photochemically and electrochemically, the oxo core formed photochemically must rapidly equilibrate with Te(IV)-(OH)2. Calculations on the bis(hydroxy) versus oxo species further corroborate that the equilibration is rapid and the spectra of the two species are similar. To further explore Te(IV) cores, two novel compounds, Te(IV)-Cl2 and Te(IV)-Br2, were synthesized. Characterization of Te(IV)-X2 was simplified because these cores have no analogue to the Te(IV)-(O)/Te(IV)-(OH)2 equilibrium. This work provides insights into the photophysical and electrochemical behavior of Te analogues of chalcogenoxanthylium dyes, which are relevant for a broad range of photochemical applications.
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Mixed matrix materials (MMMs) containing metal-organic framework (MOF) nanoparticles are attractive for membrane carbon capture. Particularly, adding <5 mass % MOFs in polymers dramatically increased gas permeability, far surpassing the Maxwell model's prediction. However, no sound mechanisms have been offered to explain this unusual low-loading phenomenon. Herein, we design an ideal series of MMMs containing polyethers (one of the leading polymers for CO2/N2 separation) and discrete metal-organic polyhedra (MOPs) with cage sizes of 2-5 nm. Adding 3 mass % MOP-3 in a polyether increases the CO2 permeability by 100% from 510 to 1000 Barrer at 35 °C because of the increased gas diffusivity. No discernible changes in typical physical properties governing gas transport properties are detected, such as glass transition temperature, fractional free volume, d-spacing, etc. We hypothesize that this behavior is attributed to fractal-like networks formed by highly porous MOPs, and for the first time, we validate this hypothesis using small-angle X-ray scattering analysis.
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Prussian blue (PB) and its analogues are promising materials for electrochemical energy storage, yet their use in flow-type devices is limited by their lack of redox responsiveness as colloidal suspensions. We have investigated the redox chemistry amine functionalization of PB along with its Cu analogue (CuPBA). No redox response of colloidal PB was observed and suspensions of CuPBA formed films on electrode surfaces with and without applied potentials; the films were redox-active but the material that remained suspended in solution did not participate in redox chemistry. Propylamine (pa), ethylenediamine (en), or tetramethylethylenediamine (TMEDA) were added in an attempt to maintain well dispersed suspensions through nanoparticle surface functionalization. Propylamine modifications resulted in a loss of the CuPBA network and subsequent precipitation of insoluble materials. Coordination of ethylenediamine prompted the formation of Cu and Fe monomers ([Cu(en)2]m+/[Fe(CN)6]n-]) that remained soluble in aqueous electrolytes. In the absence of supporting electrolytes, these monomers formed a one-dimensional (1D) polymeric structure (Cu2Fe-1D). TMEDA modification preserved the CuPBA extended structure with only modest precipitate formation over 30 min. The redox responsiveness of these suspensions depended on conditions; in 1 M KCl, no redox chemistry was observed for the CuPBA. In pH 4 potassium hydrogen phthalate buffer, a signal was observed that was attributed to the Fe centers of CuPBA. Under these conditions, the material precipitated in â¼15 min and the signal was lost. Although the Fe centers in these networks are redox-active, additional work is needed to realize longer-term redox activity and stability. Ligand modifications can alter the properties of these networks but within a given ligand class, e.g., amines, the effects can vary greatly from the deconstruction of the framework to preventing film formation.
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Self-assembled metallacyles and cages formed via coordination chemistry have been used as catalysts to enforce 4H+/4e- reduction of oxygen to water with an emphasis on attenuating the formation of hydrogen peroxide. That said, the kinetically favored 2H+/2e- reduction to H2O2 is critically important to industry. In this work we report the synthesis, characterization, and electrochemical benchmarking of a hexa-porphyrin cube which catalyses the electrochemical reduction of molecular oxgyen to hydrogen peroxide. An established sub-component self-assembly approach was used to synthesize the cubic free-base porphryin topologies from 2-pyridinecarboxaldehyde, tetra-4-aminophenylporphryin (TAPP), and Fe(OTf)2 (OTf- = trifluoromethansulfonate). Then, a tandem metalation/transmetallation was used to introduce Co(II) into the porphyrin faces of the cube, and exchange with the Fe(II) cations at the vertices, furnishing a tetrakaideca cobalt cage. Electron paramagnetic resonance studies on a Cu(II)/Fe(II) analogue probed radical interactions which inform on electronic structure. The efficacy and selectivity of the CoCo-cube as a catalyst for hydrogen peroxide generation was investigated using hydrodynamic voltammetry, revealing a higher selectivity than that of a mononuclear Co(II) porphyrin (83% versus ~50%) with orders of magnitude enhancement in standard rate constant (ks = 2.2 × 102 M-1s-1 versus ks = 3 × 100 M-1s-1). This work expands the use of coordination-driven self-assembly beyond ORR to water by exploiting post-synthetic modification and structural control that is associated with this synthetic method.
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The chemistry of zirconium-based metal-organic polyhedra (ZrMOPs) is often limited by their poor solubilities. Despite their attractive features-including high yielding and facile syntheses, predictable topologies, high stability, and tunability-problematic solubilities have caused ZrMOPs to be under-studied and under-applied. Although these cages have been synthesized with a wide variety of carboxylate-based bridging ligands, we explored a new method for ZrMOP functionalization via node-modification, which we hypothesized could influence solubility. Herein, we report ZrMOPs with benzyl-, vinylbenzyl-, and trifluoromethylbenzyl-pendant groups decorating cyclopentadienyl moieties. The series was characterized by 1H/19F NMR, high-resolution mass spectrometry, infrared spectroscopy, and single-crystal X-ray diffraction. The effects of node functionalities on ZrMOP solubility were quantified using inductively coupled plasma mass spectrometry. Substitution caused a decrease in water solubility, but for certain organic solvents, e.g. DMF, solubility could be enhanced by â¼20×, from 16 µM for the unfunctionalized cage to 310 µM for the vinylbenzyl- and trifluoromethylbenzyl-cages.
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Cofacial porphyrin catalysts for the Oxygen Reduction Reaction (ORR) formed via coordination-driven self-assembly have so far been limited to designs with fourfold symmetry, where four molecular clips bridge two porphyrin sites. We have synthesized six PynPhm (Py = pyridyl, Ph = phenyl) metalloporphyrin prisms (Co2+, Zn2+) bridged by molecular clips containing two Rh3+ centers. Four of these structures are lower symmetry, with the Py3Ph and Py2Ph2 prisms containing three and two molecular clips, respectively. The Co2+ species were evaluated for their ORR activity. Cyclic and hydrodynamic voltammetry studies of heterogeneous catalyst inks in aqueous media revealed marked differences in selectivity from â¼5% (Py3Ph) to â¼37% (Py2Ph2) for the formation of H2O2. The single-crystal X-ray structure of the Zn2 Py2Ph2 prism shows an offset between the porphyrin faces. This structural feature may be responsible for the change in selectivity, consistent with previous studies of covalently tethered cofacial porphyrins that have shown that geometry is a critical determinant of two-electron/two-proton versus four-electron/four-proton pathways. Extraction of standard rate constants ks for the ORR revealed a cofacial enhancement of â¼2 orders of magnitude over mononuclear Co2+ tetrapyridyl porphyrin. Even though all the prisms described here use the same molecular clip, the resultant structures, and thus the reactivity for the ORR, differ significantly based on the number and orientation of pyridyl donor groups on the porphyrins, highlighting how coordination-driven self-assembly can be used to rapidly tune dinuclear catalysts.
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We report the electrocatalytic Oxygen Reduction Reaction on a rigid Co(II) porphyrin prism scaffold bridged by Ag(I) ions. The reactivity of this scaffold differs significantly from previous prism catalysts in that its selectivity is similar to that of monomer (â¼35% H2O) yet it displays sluggish kinetics, with an order of magnitude lower ks of â¼0.5 M-1 s-1. The deleterious cofacial effect is not simply due to metal-metal separation, which is similar to our most selective prism catalysts. Instead we conclude the structural rigidity is responsible for these differences.
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Porfirinas , Porfirinas/química , Oxirredução , Catálise , Cinética , Oxigênio/químicaRESUMO
The utilization of deep blue phosphorescent materials in high-performance displays and solid-state lighting requires high quantum efficiencies and color purities. Here, we describe the preparation and luminescent properties of novel platinum triplet emitters featuring cyclometalated N-pyridyl-carbazole ligands functionalized with closo-monocarborane clusters [CB11H12]-. All reported complexes were fully characterized by using standard small molecule techniques (UV-vis, cyclic voltammetry, nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HRMS)), and their solid-state structures were elucidated by X-ray diffraction. These platinum phosphors emit in the blue region of the visible wavelength spectrum in both the solid and solution states. Complex 4a exhibits the highest luminous efficiency at λem = 439 nm with a photoluminescent quantum yield (PLQY) of 60% by dispersing in a PMMA matrix. Electrochemical and computational studies of complexes 4a and 4b revealed that the blue phosphorescence originates mainly from intraligand 3π â π* (3ILCT) transitions with relatively small 3MLCT mixing. A deep-blue OLED containing 4a as the light-emitting dopant was successfully fabricated using a solution-processed method, and the device exhibited blue photoluminescence with CIE coordinates of (0.17, 0.15) and a maximum external quantum efficiency (EQEmax) value of 6.2%. This article represents the pioneering study of a deep blue PhOLED using a Pt complex bearing a closo-monocarborane anion substituent, providing a new avenue into the preparation of novel triplet emitters based on boron-rich cluster anions.
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A metal-organic polyhedron (MOP) with four paramagnetic Fe(III) centers was studied as a magnetic resonance imaging (MRI) probe. The MOP was characterized in solution by using electron paramagnetic resonance (EPR), UV-visible (UV-vis) spectroscopies, Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry, and in the solid state with single-crystal X-ray diffraction. Water proton T1 relaxation properties were examined in solution and showed significant enhancement in the presence of human serum albumin (HSA). The r1 relaxivities in the absence and presence of HSA were 8.7 mM-1 s-1 and 21 mM-1 s-1, respectively, per molecule (2.2 mM-1 s-1 and 5.3 mM-1 s-1 per Fe) at 4.7 T, 37 °C. In vivo studies of the iron MOP show strong contrast enhancement of the blood pool even at a low dose of 0.025 mmol/kg with prolonged residence in vasculature and clearance through the intestinal tract of mice. The MOP binds strongly to serum albumin and shows comparable accumulation in a murine tumor model as compared to a covalently linked Gd-HSA contrast agent.
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Meios de ContrasteRESUMO
Among the many challenges in medicine, the treatment and cure of cancer remains an outstanding goal given the complexity and diversity of the disease. Nanotheranostics, the integration of therapy and diagnosis in nanoformulations, is the next generation of personalized medicine to meet the challenges in precise cancer diagnosis, rational management and effective therapy, aiming to significantly increase the survival rate and improve the life quality of cancer patients. Different from most conventional platforms with unsatisfactory theranostic capabilities, supramolecular cancer nanotheranostics have unparalleled advantages in early-stage diagnosis and personal therapy, showing promising potential in clinical translations and applications. In this review, we summarize the progress of supramolecular cancer nanotheranostics and provide guidance for designing new targeted supramolecular theranostic agents. Based on extensive state-of-the-art research, our review will provide the existing and new researchers a foundation from which to advance supramolecular cancer nanotheranostics and promote translationally clinical applications.
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Antineoplásicos/química , Nanoestruturas/química , Neoplasias/diagnóstico , Neoplasias/terapia , Medicina de Precisão/métodos , Nanomedicina Teranóstica/métodos , Animais , Antineoplásicos/farmacologia , Transporte Biológico , DNA/química , Humanos , Lipossomos/química , Nucleotídeos/química , Compostos Organometálicos/química , Proteínas/químicaRESUMO
We assembled eight cofacial porphyrin prisms using MTPyP (M = Co(II) or Zn(II), TPyP = 4-tetrapyridylporphyrin) and functionalized ruthenium-based "molecular clips" using coordination-driven self-assembly. Our approach allows for the rapid synthesis of these architectures in isolated yields as high as 98% for the assembly step. Structural and reactivity studies provided a deeper understanding of the role of the building blocks on the oxygen reduction reaction (ORR). Catalytic efficacy was probed by using cyclic and hydrodynamic voltammetry on heterogeneous catalyst inks in aqueous media. The reported prisms showed outstanding selectivity (>98%) for the kinetically hindered 4e-/4H+ reduction of O2 to H2O over the kinetically more accessible 2e-/2H+ reduction to H2O2. Furthermore, we have demonstrated significant cofacial enhancement in the observed catalytic rate constant ks (â¼5 orders of magnitude) over the mononuclear analogue. We conclude that the steric bulk of the clip plays an important role in the structural dynamics of these prisms, which in turn modulates the ORR reactivity with respect to selectivity and kinetics.
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An anionic iron(II) tetrahedral molecular cage (FeMOP) was studied for its ability to interact with various per- and polyfluoroalkyl substances (PFASs) in aqueous media. Liquid chromatography tandem mass spectrometry revealed that longer-chain-length (more than six carbons) perfluorocarboxylic, -sulfonic, and fluorotelomers were removed from solution. In contrast, the steric bulk of N-ethyl substituted fluorosulfonamido acetic acid PFASs hindered association with the cage. Solution binding studies in D2O using 19F nuclear magnetic resonance (NMR) titrations and a Job plot show a 1:1 binding stoichiometry for perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) with an association constant (Ka) of <103 and thus a favorable free energy of association (ΔG°). Perfluorononanoic acid (PFNA), on the other hand, forms an insoluble host-guest complex with FeMOP with a 1:1 host-guest ratio. Variable temperature (VT) NMR was used to determine the thermodynamic parameters of binding for a 1:1 FeMOP/PFHpA complex in water using a Curie-like model for fast-exchange processes. The extracted parameters suggest a low binding interaction (Ka < 103) driven by an increase in entropy from cage desolvation upon guest binding. The solid-state host-guest complexes formed from solution complexation of PFHxA, PFHpA, and PFNA into the cage were characterized by infrared spectroscopy (FT-IR) and powder X-ray diffraction (PXRD) methods. FT-IR studies suggest an interaction between the fluorocarbon groups of PFASs to the phenylsulfonate functional groups of the ligand. A docking model predicted by computation also indicates this interaction may occur, with the PFASs adsorbing onto the surface of the cage rather than forming a true host-guest complex within the internal cavity. PXRD studies reveal a crystal packing of the complex that is very similar to that of the water-treated FeMOP, with the exception of 1:2 FeMOP/PFNA and 1:1 and 2:1 FeMOP/PFHpA.
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In this work, we investigate the self-assembly between Ag(I) and Au(I) centers and pyridyl donors to form hexagonal metallacycles and related linear complexes. The precipitation of hexagonal metallacycles upon assembly in chloroform/methanol mixtures results in high solid-state photo-stability. Whereas, the Ag(I) species have fast kinetics and high formation constants in acetone, this solvent interferes in the formation of the analogous Au(I) complexes. The photophysical properties of this suite of metallacycles was investigated including steady-state absorption, emission, and time-resolved lifetime measurements. All ligands and hexagons exhibited ligand-centered singlet emissions with ground-state absorption and emission perturbed upon coordination. The ligand-based fluorescent photoluminescence was affected by the heavy-atom effect when halide or metals are present, attenuating quantum yields as evidenced by increases in the experimentally measured non-radiative rate constants. The formation of group 11 metallacycles is motivated by their potential applications in mixed-matrix materials wherein metal ions can interact with substrate to facilitate separations chemistry with reduced energy requirements, in particular the isolation of ethylene and light olefins. Existing processes involve cryogenic distillation, an energy intensive and inefficient method.
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The local environment surrounding luminophores can significantly influence their photophysical properties. Herein, we report the self-assembly of a highly emissive platinum(II)-based metallacage. In order to accommodate the connectivity of the platinum(II) building block used in the self-assembly process, the luminophore-containing building block adopts a highly twisted geometry relative to its free form, leading to the emergence of an emissive transition with a radiative rate constant an order of magnitude higher than that of the free luminophore. This increased rate constant is the primary driver for the 10-fold increase in quantum yield from 4.2% to 40%. Model complexes with platinum or methyl groups bound to the nitrogen were synthesized. These complexes had lower quantum yields (10% and non-emissive, respectively) due mainly to decreases in radiative rate constants. Computational studies were conducted and indicated that the excited state of the ensembles, as well as the model complexes, is a result of charge transfer to the pyridyl groups, in contrast to the free luminophore, which involves the diphenyl sulfone moiety. The differences in quantum yields can be explained by a twist in the chromophore upon coordination of platinum or methylation on the pyridyl group, leading to intersystem crossing to a triplet state. This state then becomes more emissive with the addition of platinum, which increases the radiative rate constant via the heavy atom effect. The formation of a metallacage also decreases the non-radiative rate constant by inhibiting the intramolecular motions of the incorporated luminophore.
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Complexos de Coordenação/síntese química , Substâncias Luminescentes/síntese química , Fenotiazinas/química , Platina/química , Complexos de Coordenação/química , Luminescência , Substâncias Luminescentes/química , Estrutura Molecular , Teoria QuânticaRESUMO
Photodynamic therapy is an effective alternative to traditional treatments due to its minimally invasive nature, negligible systemic toxicity, fewer side effects, and avoidance of drug resistance. However, it is still challenging to design photosensitizers with high singlet oxygen (1O2) quantum yields (QY) due to severe aggregation of the hydrophobic photosensitizers. Herein, we developed a discrete organoplatinum(II) metallacage using therapeutic cis-(PEt3)2Pt(OTf)2 as the building block to improve the 1O2 QY, thus achieving synergistic anticancer efficacy. The metallacage-loaded nanoparticles (MNPs) with tri-modality imaging capability allow precise diagnosis of tumor and real-time monitoring the delivery, biodistribution, and excretion of the MNPs. MNPs exhibited excellent anti-metastatic effect and superior anti-tumor performance against U87MG, drug resistant A2780CIS, and orthotopic tumor models, ablating the tumors without recurrence after a single treatment. Gene chip analyses confirmed the contribution of different therapeutic modalities to the tumor abrogation. This supramolecular platform holds potential in precise cancer theranostics.
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Neoplasias Hepáticas/terapia , Compostos Organoplatínicos/química , Fotoquimioterapia , Nanomedicina Teranóstica , Animais , Antineoplásicos/farmacologia , Antineoplásicos/uso terapêutico , Linhagem Celular Tumoral , Sistemas de Liberação de Medicamentos , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Sinergismo Farmacológico , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Humanos , Neoplasias Hepáticas/genética , Neoplasias Hepáticas/patologia , Neoplasias Pulmonares/secundário , Camundongos Endogâmicos BALB C , Camundongos Nus , Nanopartículas/química , Espectrometria de FluorescênciaRESUMO
We report a suite of coordination-driven self-assembled prisms for heterogeneous electrocatalytic oxygen reduction (ORR) differing in the molecular clips linking two porphyrin faces in a cofacial arrangement. ORR activities and selectivities of monomeric CoTPyP along with cofacial prisms Ox-Co, Oxa-Co, and Benzo-Co were probed using cyclic voltammetry and rotating ring-disk techniques. All species were immobilized as heterogeneous catalysts on glassy carbon electrodes using a Nafion ink method. The selectivities of Ox-Co, Oxa-Co, and Benzo-Co prisms towards H2 O as determined by RRDE were 87, 97, and 75 %, respectively. The current density of the Oxa-Co plateaus at five times that of Pt/C when normalized per Co/Pt. The high synthetic yield (79 %), competitive overpotential (η ≈800â mV) and high selectivity (%H2 O ≈97 %) of the Oxa-Co highlights how self-assembly can be used to address multi-electron multi-proton transformations using polynuclear catalysts.
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Light-emitting supramolecular coordination complexes (SCCs) have been widely studied for applications in the chemical and biological sciences. Herein, we report the coordination-driven self-assembly of two highly emissive platinum(II) supramolecular triangles (1 and 2) containing BODIPY-based bridging ligands. The metallacycles exhibit favorable anticancer activities against HeLa cells (IC50 of 6.41 and 2.11 µM). The characteristic â¼570 nm fluorescence of the boron dipyrromethene (BODIPY) moieties in the metallacycles permits their intracellular visualization using confocal microscopy. Additionally, the BODIPY fluorophore is an excellent photodynamic agent, making the metallacycles as ideal therapeutics for photodynamic therapy (PDT) and chemotherapy. In vitro studies demonstrate that the combination indexes against HeLa cells are 0.56 and 0.48 for 1 and 2, respectively, confirming their synergistic anticancer effect. More importantly, these SCCs also exhibit superior anticancer efficacy toward cisplatin-resistant A2780cis cell line by combining PDT and chemotherapy, showing promise in overcoming drug resistance. This study exploits a multicomponent approach to self-assembled metallacages that enables design of effective theranostic agents wherein the platinum acceptors are toxic chemotherapeutics and the BODIPY donors are imaging probes and photosensitizers. Since each piece may be independently tuned, i.e., Pt(II) polypyridyl fragment swapped for Pt(II) phosphine, the activity may be optimized without a total redesign of the system.
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Antineoplásicos/farmacologia , Compostos de Boro/farmacologia , Complexos de Coordenação/farmacologia , Corantes Fluorescentes/farmacologia , Compostos Organoplatínicos/farmacologia , Fármacos Fotossensibilizantes/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Antineoplásicos/efeitos da radiação , Apoptose/efeitos dos fármacos , Compostos de Boro/síntese química , Compostos de Boro/química , Compostos de Boro/efeitos da radiação , Linhagem Celular Tumoral , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Complexos de Coordenação/efeitos da radiação , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/química , Corantes Fluorescentes/efeitos da radiação , Humanos , Luz , Microscopia Confocal , Nanopartículas/química , Necrose/induzido quimicamente , Compostos Organoplatínicos/síntese química , Compostos Organoplatínicos/química , Compostos Organoplatínicos/efeitos da radiação , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação , Nanomedicina TeranósticaRESUMO
Herein we report the synthesis and characterization of two diphosphazane (P-N-P) ligands, along with their corresponding novel palladium and platinum complexes. Compounds were characterized by FTIR and NMR spectroscopy, single crystal X-ray diffraction (SC-XRD), and powder X-ray diffraction (PXRD)), as well as mass spectrometry. The Pd(II) complex of the p-phenyldiphosphazane was shown to effectively and efficiently catalyze Suzuki-Miyaura cross-coupling reactions between a variety of substrates. Yields were as high as 96%, with reaction times as short as 15 min at room temperature and open to air. No additional supporting ligands, such as triphenylphosphine, were needed. The work reported here expands the use of phosphazane ligands to support catalytic centers and provides an understanding of phosphazane metal-ligand bonding interactions (specifically diphosphazanes).
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Discrete metal-organic polyhedra (MOPs) containing copper(ii), palladium(ii), and iron(ii) nodes were synthesized as fillers for mixed-matrix materials (MMMs) with a polyvinylidine fluoride (PVDF) polymer phase and contrasted against an MMM containing a metal-organic framework, MOF-5. When a given MOP was soluble in the precursor solutions, the resulting MMMs were thin, flexible, and homogeneous based on microscopy and SEM imaging. Analogous MMM formation using either insoluble MOPs or the inherent insoluble MOF-5 showed a higher degree of phase separation and inhomogeneity. Even when a MOP was not fully soluble, a significant particle size decrease was observed in contrast to the MOF-5 materials wherein the crystallites remained largely intact. This is a consequence of solubilizing the MOP fillers into the polymer solvent. The crystallinity and thermal stabilities of the MMMs were compared to pure PVDF using powder X-ray diffraction, and differential scanning calorimetry, indicating that the incorporation of MOPs both decreased overall crystallinity as well as increased thermal stability. In addition, MMMs containing PdMOP and FeMOP showed improved gas permeabilities relative to pure PVDF for H2, N2, CH4, and CO2, with the 10 wt% FeMOP membrane more selective for CO2 over N2 and H2.
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Here we report on a scanning tunnelling microscopy (STM) investigation on the self-assembly of C3- and C2-symmetric molecules at the solution/graphite interface. 1,3,5-tris((E)-2-(pyridin-4-yl)vinyl)benzene and 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethane are used as model systems. These molecules displayed a concentration dependent self-assembly behaviour on graphite, resulting in highly ordered supramolecular structures, which are stabilized jointly by van der Waals substrate-adsorbate interactions and in-plane intermolecular H-bonding. Denser packing is obtained when applying a relatively high concentration solution to the basal plane of the surface whereas a less dense porous network is observed upon lowering the concentration. We show that the molecular conformation does not influence the stability of the self-assembly and a twisted molecule can pack into dense and porous architectures under the concentration effect.