Polymer-Coated Covalent Organic Frameworks as Porous Liquids for Gas Storage.

Several synthetic methods have recently emerged to develop high-surface-area solid-state organic framework-based materials into free-flowing liquids with permanent porosity. The fluidity of these porous liquid (PL) materials provides them with advantages in certain storage and transport processes. However, most framework-based materials necessitate the use of cryogenic temperatures to store weakly bound gases such as H2, temperatures where PLs lose their fluidity. Covalent organic framework (COF)-based PLs that could reversibly form stable complexes with H2 near ambient temperatures would represent a promising development for gas storage and transport applications. We report here the development, characterization, and evaluation of a material with these remarkable characteristics based on Cu(I)-loaded COF colloids. Our synthetic strategy required tailoring conditions for growing robust coatings of poly(dimethylsiloxane)-methacrylate (PDMS-MA) around COF colloids using atom transfer radical polymerization (ATRP). We demonstrate exquisite control over the coating thickness on the colloidal COF, quantified by transmission electron microscopy and dynamic light scattering. The coated COF material was then suspended in a liquid polymer matrix to make a PL. CO2 isotherms confirmed that the coating preserved the general porosity of the COF in the free-flowing liquid, while CO sorption measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed the preservation of Cu(I) coordination sites. We then evaluated the gas sorption phenomenon in the Cu(I)-COF-based PLs using DRIFTS and temperature-programmed desorption measurements. In addition to confirming that H2 transport is possible at or near mild refrigeration temperatures with these materials, our observations indicate that H2 diffusion is significantly influenced by the glass-transition temperature of both the coating and the liquid matrix. The latter result underscores an additional potential advantage of PLs in tailoring gas diffusion and storage temperatures through the coating composition.

Enhanced hydrogen bonding via epoxide-functionalization restricts mobility in poly(ethylenimine) for CO2 capture.

Free energy sampling, deep potential molecular dynamics, and characterizations provide insights into the impact of epoxide-functionalization on the hydrogen bonding and mobility of poly(ethylenimine), a promising CO2 sorbent. These findings rationalize the anti-degradation effects of epoxide functionalization and open up new avenues for designing more durable CO2 sorbents.

Phototriggered Desorption of Hydrogen, Ethylene, and Carbon Monoxide from a Cu(I)-Modified Covalent Organic Framework.

Materials that are capable of adsorbing and desorbing gases near ambient conditions are highly sought after for many applications in gas storage and separations. While the physisorption of typical gases to high surface area covalent organic frameworks (COFs) occurs through relatively weak intermolecular forces, the tunability of framework materials makes them promising candidates for tailoring gas sorption enthalpies. The incorporation of open Cu(I) sites into framework materials is a proven strategy to increase gas uptake closer to ambient conditions for gases that are capable of π-back-bonding with Cu. Here, we report the synthesis of a Cu(I)-loaded COF with subnanometer pores and a three-dimensional network morphology, namely Cu(I)-COF-301. This study focused on the sorption mechanisms of hydrogen, ethylene, and carbon monoxide with this material under ultrahigh vacuum using temperature-programmed desorption and Kissinger analyses of variable ramp rate measurements. All three gases desorb near or above room temperature under these conditions, with activation energies of desorption (E des) calculated as approximately 29, 57, and 68 kJ/mol, for hydrogen, ethylene, and carbon monoxide, respectively. Despite these strong Cu(I)-gas interactions, this work demonstrated the ability to desorb each gas on-demand below its normal desorption temperature upon irradiation with ultraviolet (UV) light. While thermal imaging experiments indicate that bulk photothermal heating of the COF accounts for some of the photodriven desorption, density functional theory calculations reveal that binding enthalpies are systematically lowered in the COF-hydrogen matrix excited state initiated by UV irradiation, further contributing to gas desorption. This work represents a step toward the development of more practical ambient temperature storage and efficient regeneration of sorbents for applications with hydrogen and π-accepting gases through the use of external photostimuli.

Covalently Bound Nitroxyl Radicals in an Organic Framework.

A series of covalent organic framework (COF) structures is synthesized that possesses a tunable density of covalently bound nitroxyl radicals within the COF pores. The highest density of organic radicals produces an electron paramagnetic resonance (EPR) signal that suggests the majority of radicals strongly interact with other radicals, whereas for smaller loadings the EPR signals indicate the radicals are primarily isolated but with restricted motion. The dielectric loss as determined from microwave absorption of the framework structures compared with an amorphous control suggests that free motion of the radicals is inhibited when more than 25% of available sites are occupied. The ability to tune the mode of radical interactions and the subsequent effect on redox, electrical, and optical characteristics in a porous framework may lead to a class of structures with properties ideal for photoelectrochemistry or energy storage.

Close Packing of Nitroxide Radicals in Stable Organic Radical Polymeric Materials.

The relationship between the polymer network and electronic transport properties for stable radical polymeric materials has come under investigation owing to their potential application in electronic devices. For the radical polymer poly(2,2,6,6-tetramethylpiperidine-4-yl-1-oxyl methacrylate), it is unclear whether the radical packing is optimal for charge transport partially because the relationship between radical packing and molecular structure is not well-understood. Using the paramagnetic nitroxide radical as a probe of the polymer and synthetic techniques to control the radical concentration on the methyl methacrylate backbone, we investigate the dependence of radical concentration on molecular structure. The electron paramagnetic resonance data indicate that radicals in the PTMA assume a closest approach distance to each other when more than 60% of the backbone is populated with radical pendant groups. Below 60% coverage, the polymer rearranges to accommodate larger radical-radical spacing. These findings are consistent with theoretical calculations and help explain some experimentally determined electron-transport properties.

Quenching of the perylene fluorophore by stable nitroxide radical-containing macromolecules.

Stable nitroxide radical bearing organic polymer materials are attracting much attention for their application as next generation energy storage materials. A greater understanding of the inherent charge transfer mechanisms in such systems will ultimately be paramount to further advancements in the understanding of both intrafilm and interfacial ion- and electron-transfer reactions. This work is focused on advancing the fundamental understanding of these dynamic charge transfer properties by exploiting the fact that these species are efficient fluorescence quenchers. We systematically incorporated fluorescent perylene dyes into solutions containing the 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) radical and controlled their interaction by binding the TEMPO moiety into macromolecules with varying morphologies (e.g., chain length, density of radical pendant groups). In the case of the model compound, 4-oxo-TEMPO, quenching of the perylene excited state was found to be dominated by a dynamic (collisional) process, with a contribution from an apparent static process that is described by an ∼2 nm quenching sphere of action. When we incorporated the TEMPO unit into a macromolecule, the quenching behavior was altered significantly. The results can be described by using two models: (A) a collisional quenching process that becomes less efficient, presumably due to a reduction in the diffusion constant of the quenching entity, with a quenching sphere of action similar to 4-oxo-TEMPO or (B) a collisional quenching process that becomes more efficient as the radius of interaction grows larger with increasing oligomer length. This is the first study that definitively illustrates that fluorophore quenching by a polymer system cannot be explained using merely a classical Stern-Volmer approach but rather necessitates a more complex model.

Semi-random vs Well-Defined Alternating Donor-Acceptor Copolymers.

The influence of backbone composition on the physical properties of donor-acceptor (D-A) copolymers composed of varying amounts of benzodithiophene (BDT) donor with the thienoisoindoledione (TID) acceptor is investigated. First, the synthesis of bis- and tris-BDT monomers is reported; these monomers are subsequently used in Stille copolymerizations to create well-defined alternating polymer structures with repeating (D-A), (D-D-A), and (D-D-D-A) units. For comparison, five semi-random D-A copolymers with a D:A ratio of 1.5, 2, 3, 4, and 7 were synthesized by reacting trimethyltin-functionalized BDT with various ratios of iodinated BDT and brominated TID. While the HOMO levels of all the resultant polymers are very similar, a systematic red shift in the absorbance spectra onset of the D-A copolymer films from 687 to 883 nm is observed with increasing acceptor content, suggesting the LUMO can be fine-tuned over a range of 0.4 eV. When the solid-state absorbance spectra of well-defined alternating copolymers are compared to those of semi-random copolymers with analogous D:A ratios, the spectra of the alternating copolymers are significantly more red-shifted. Organic photovoltaic device efficiencies show that the semi-random materials all outperform the well-defined alternating copolymers, and an optimal D:A ratio of 2 produces the highest efficiency. Additional considerations concerning fine-tuning the lifetimes of the photoconductance transients of copolymer:fullerene films measured by time-resolved microwave conductivity are discussed. Overall, the results of this work indicate that the semi-random approach is a powerful synthetic strategy for fine-tuning the optoelectronic and photophysical properties of D-A materials for a number of systematic studies, especially given the ease with which the D:A ratios in the semi-random copolymers can be tuned.

Highly active copper-based catalyst for atom transfer radical polymerization.

Atom transfer radical polymerization (ATRP) generally requires a catalyst/initiator molar ratio of 0.1 to 1 and catalyst/monomer molar ratio of 0.001 to 0.01 (i.e., catalyst concentration: 1000-10,000 ppm versus monomer). Herein, we report a new copper-based complex CuBr/N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) as a versatile and highly active catalyst for acrylic, methacrylic, and styrenic monomers. The catalyst mediated ATRP at a catalyst/initiator molar ratio of 0.005 and produced polymers with well-controlled molecular weights and low polydispersities. ATRP occurred even at a catalyst/initiator molar ratio as low as 0.001 with copper concentration in the produced polymers as low as 6-8 ppm (catalyst/monomer molar ratio = 10(-5)). The catalyst structures were studied by X-ray diffraction and NMR spectroscopy. The activator CuIBr/TPEN existed in solution as binuclear and mononuclear complexes in equilibrium but as a binuclear complex in its single crystals. The deactivator CuIIBr2/TPEN complex was mononuclear. High stability and appropriate KATRP (ATRP equilibrium constant) were found crucial for the catalyst working under high dilution or in coordinating solvents/monomers. This provides guidance for further design of highly active ATRP catalysts.

Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents.

The concept of initiators for continuous activator regeneration (ICAR) in atom transfer radical polymerization (ATRP) is introduced, whereby a constant source of organic free radicals works to regenerate the Cu(I) activator, which is otherwise consumed in termination reactions when used at very low concentrations. With this technique, controlled synthesis of polystyrene and poly(methyl methacrylate) (Mw/Mn < 1.2) can be implemented with catalyst concentrations between 10 and 50 ppm, where its removal or recycling would be unwarranted for many applications. Additionally, various organic reducing agents (derivatives of hydrazine and phenol) are used to continuously regenerate the Cu(I) activator in activators regenerated by electron transfer (ARGET) ATRP. Controlled polymer synthesis of acrylates (Mw/Mn < 1.2) is realized with catalyst concentrations as low as 50 ppm. The rational selection of suitable Cu complexing ligands {tris[2-(dimethylamino)ethyl]amine (Me6TREN) and tris[(2-pyridyl)methyl]amine (TPMA)} is discussed in regards to specific side reactions in each technique (i.e., complex dissociation, acid evolution, and reducing agent complexation). Additionally, mechanistic studies and kinetic modeling are used to optimize each system. The performance of the selected catalysts/reducing agents in homo and block (co)polymerizations is evaluated.