James P. Blinco

Experimental and Theoretical Studies of the Redox Potentials of Cyclic Nitroxides

The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrrolidine, piperidine, isoindoline, and azaphenalene) were determined experimentally by cyclic voltammetry in acetonitrile, and also via high-level ab initio molecular orbital calculations. It is shown that the potentials are influenced by the type of ring system, ring substituents and/or groups surrounding the radical moiety. For the pyrrolidine, piperidine, and isoindolines there is excellent agreement (mean absolute deviation of 0.05 V) between the calculated and experimental oxidation potentials; for the azaphenalenes, however, there is an extraordinary discrepancy (mean absolute deviation of 0.60 V), implying that their one-electron oxidation might involve additional processes not considered in the theoretical calculations. This recently developed azaphenalene class of nitroxide represents a new variant of a nitroxide ring fused to an aromatic system and details of the synthesis of five derivatives involving differing aryl substitution are also presented.

Profluorescent Nitroxides as Sensitive Probes of Oxidative Change and Free Radical Reactions

This paper presents a review on the use of tethered nitroxide–fluorophore molecules as probes of oxidative change and free radical generation and reaction. The proximity of the nitroxide free radical to the fluorophore suppresses the normal fluorescence emission process. Nitroxide free radical scavenging, metabolism or redox chemistry return the system to its natural fluorescent state and so these tethered nitroxide–fluorophore molecules are described as being profluorescent. A survey of profluorescent nitroxides found in the literature is provided as well as background on the mechanism of action and applications of these compounds as fluorometric probes within the fields of biological, materials and environmental sciences.

Diels–Alder Reactions as an Efficient Route to High Purity Cyclic Polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels-Alder reaction yielding a high purity cyclic product.

Computational Design of Cyclic Nitroxides as Efficient Redox Mediators for Dye‐Sensitized Solar Cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E(ox)°, and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs.

Electron spin-lattice relaxation of nitroxyl radicals in temperature ranges that span glassy solutions to low-viscosity liquids.

Electron spin-lattice relaxation rates, 1/T1, at X-band of nitroxyl radicals (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidin-1-oxyl and 3-carbamoyl-2,2,5,5-tetramethylpyrrolin-1-oxyl) in glass-forming solvents (decalin, glycerol, 3-methylpentane, o-terphenyl, 1-propanol, sorbitol, sucrose octaacetate, and 1:1 water:glycerol) at temperatures between 100 and 300K were measured by long-pulse saturation recovery to investigate the relaxation processes in slow-to-fast tumbling regimes. A subset of samples was also studied at lower temperatures or at Q-band. Tumbling correlation times were calculated from continuous wave lineshapes. Temperature dependence and isotope substitution (2H and 15N) were used to distinguish the contributions of various processes. Below about 100K relaxation is dominated by the Raman process. At higher temperatures, but below the glass transition temperature, a local mode process makes significant contributions. Above the glass transition temperature, increased rates of molecular tumbling modulate nuclear hyperfine and g anisotropy. The contribution from spin rotation is very small. Relaxation rates at X-band and Q-band are similar. The dependence of 1/T1 on tumbling correlation times fits better with the Cole-Davidson spectral density function than with the Bloembergen-Purcell-Pound model.

Impact of molecular size on electron spin relaxation rates of nitroxyl radicals in glassy solvents between 100 and 300 K

Electron spin lattice relaxation rates were measured for 12 nitroxyls with molecular weights between 144 and 438, and for galvinoxyl, 1,3-bisdiphenylene-2-phenylallyl (BDPA), and 2,2-diphenyl-1-picrylhydrazyl (DPPH) in glassy sucrose octaacetate. Relaxation rates for polar nitroxyls also were measured in glassy sorbitol. Dependence on T where V eff is effective molecular volume and γ is a material-specific parameter, was used to compare processes. Values of V eff were determined based on molecular libration in glassy sucrose octaacetate (γ = 3.5), tumbling in viscous decalin at 233 K (γ = 4.7), or tumbling in heavy mineral oil (γ = 6.0). For nitroxyl relaxation there is a master curve: log(1/T 1) vs log( T) (γ = 0.89). The similarity of the values of γ for the Raman process and for the additional process that contributes at higher temperatures, and the absence of frequency dependence between X- and Q-band, support assignment of this additional process as a local mode. For these radicals the contributions from the local mode and the Raman process are correlated and follow trends in spin–orbit coupling. The temperature dependence of spin echo dephasing in sucrose octaacetate is dominated by rotation of methyl groups and by a motional process analogous to the Raman process.

(Ultra)fast catalyst-free macromolecular conjugation in aqueous environment at ambient temperature.

Tailor-made water-soluble macromolecules, including a glycopolymer, obtained by living/controlled RAFT-mediated polymerization are demonstrated to react in water with diene-functionalized poly(ethylene glycol)s without pre- or post-functionalization steps or the need for a catalyst at ambient temperature. As previously observed in organic solvents, hetero-Diels-Alder (HDA) conjugations reached quantitative conversion within minutes when cyclopentadienyl moieties were involved. However, while catalysts and elevated temperatures were previously necessary for open-chain diene conjugation, additive-free HDA cycloadditions occur in water within a few hours at ambient temperature. Experimental evidence for efficient conjugations is provided via unambiguous ESI-MS, UV/vis, NMR, and SEC data.

λ‐Orthogonal Pericyclic Macromolecular Photoligation

A photochemical strategy enabling λ-orthogonal reactions is introduced to construct macromolecular architectures and to encode variable functional groups with site-selective precision into a single molecule by the choice of wavelength. λ-Orthogonal pericyclic reactions proceed independently of one another by the selection of functional groups that absorb light of specific wavelengths. The power of the new concept is shown by a one-pot reaction of equimolar quantities of maleimide with two polymers carrying different maleimide-reactive endgroups, that is, a photoactive diene (photoenol) and a nitrile imine (tetrazole). Under selective irradiation at λ=310-350 nm, any maleimide (or activated ene) end-capped compound reacts exclusively with the photoenol functional polymer. After complete conversion of the photoenol, subsequent irradiation at λ=270-310 nm activates the reaction of the tetrazole group with functional enes. The versatility of the approach is shown by λ-orthogonal click reactions of complex maleimides, functional enes, and polymers to the central polymer scaffold.

Formation of nanoporous materials via mild retro-Diels–Alder chemistry

Poly(styrene)-block-poly(ethylene oxide) copolymers synthesized via the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and hetero Diels–Alder (HDA) cycloaddition can be cleaved in the solid state by a retro-HDA reaction occurring at 90 °C. Nanoporous films can be prepared from these polymers using a simple heating and washing procedure.

Dynamic Covalent Chemistry on Surfaces Employing Highly Reactive Cyclopentadienyl Moieties

Silicon substrates coated with a bromide-terminated silane are transformed into highly reactive, cyclopentadiene covered analogues. These surfaces undergo rapid cycloaddition reactions with various dienophile-capped polymers. Mild heating of the substrates causes the retro-Diels-Alder reaction to occur, thus reforming the reactive cyclopentadiene surface, generating an efficiently switchable surface.