Electronic effects of conjugated aryl groups on the properties and reactivities of di(arylethynyl)tetracenes.

The photochemical oxidations of acenes can cause challenges with their optoelectronic applications, such as singlet fission and organic transistors. At the same time, these reactions form the basis for many luminescent sensing schemes for 1O2. While diethynyl substitution is arguably the most widely adopted of the various substitution strategies to control oxidation and also improve solubility and processability of long acenes, the extent to which differences between the alkyne groups can influence key properties of long acenes remains largely unknown. This report therefore describes the effects of various arenes and heteroarenes on the electronic structures, optical properites, and reactivity with singlet oxygen for eight 5,12-di(arylethynyl)tetracenes. The fluorescence spectra of these tetracenes span approximately 100 nm, while their observed rate constants for reaction with singlet oxygen correlates strongly with the HOMO level, spanning one order of magnitude. They are also amenable to fluorescent materials that respond ratiometrically to singlet oxygen. Therefore, electronic effects of groups directly conjugated to ethynylacenes offer a useful chemical space for rational acene design.

Resistance to Unwanted Photo-Oxidation of Multi-Acene Molecules.

Although long acenes remain a key class of π-conjugated molecules for numerous applications, photoinduced oxidation upon exposure of the acene to light, often through sensitization of 1O2, is an important reaction requiring mitigation for most applications. In response to this ongoing challenge, this paper presents a series of four new diarylethynyl-substituted long acenes-three tetracenes and one anthradithiophene-in which the arylene pendants are either benzene, naphthalene, or anthracene. UV/vis and fluorescence spectroscopy reveals that the anthracene-substituted derivatives fluoresce poorly (Φ < 0.01). Although all four long acenes react with 1O2 at expected rates when an external photosensitizer is included and show the expected changes in fluorescence to accompany these reactions, the anthracene-substituted derivatives resist direct photoinduced oxidation. Through a combination of mechanistic experiments, we conclude that rapid nonradiative decay of the anthracene-substituted derivatives, perhaps because of inter-arene torsions that emerge in theoretical geometry optimizations, makes these compounds poor photosensitizers for 1O2 or other reactive oxygen species. This discovery opens new design possibilities for extended acene structures with improved photochemical stability.

Acenes beyond organic electronics: sensing of singlet oxygen and stimuli-responsive materials.

The spectroscopic, electronic, and geometrical properties of acenes have enabled their broad applicability in organic optoelectronics. Beyond these physical characteristics of acenes, acenes also offer characteristic and predictable reaction chemistry, especially their behavior as dienes in cycloaddition reactions. Although these cycloaddition reactions, especially those with singlet oxygen (1O2) as the dienophile, are detrimental for organic electronics, this reactivity has led to several different applications such as sensing of 1O2, the release of cytotoxic reactive oxygen species (ROS), and stimuli-responsive materials for drug delivery. The rational design of acenes in these chemically-responsive applications beyond organic optoelectronics requires an understanding of how chemical structure influences both the physical properties, such as quantum yield of emission, as well as the reactivity of acenes and their cycloadducts. Therefore, the objective of this review is to summarize how cycloaddition reactions of acenes have expanded their applications in different areas of materials chemistry, and in doing so inspire and inform the rational design of acene-based materials with applications beyond organic electronics.

Spectroscopy and Reactivity of Dialkoxy Acenes.

Photochemical oxidation of acenes can benefit or impede their function, depending on the application. Although acenes with alkoxy substituents on reactive sites are important for applications as diverse as drug delivery and organic optoelectronics, the influence of chemical structure on their photochemical oxidation remains unknown. This paper therefore describes the synthesis, spectroscopic properties, and reactivity with singlet oxygen (1 O2 ) of a series of dialkoxyacenes that vary in the number and types of fused rings in the (hetero)acene cores. Reductive alkylation of quinone precursors yielded target dialkoxyacenes with fused backbones ranging from benzodithiophene to tetracenothiophene. Trends of their experimental spectroscopic characteristics were consistent with time-dependent density functional theory (TD-DFT) calculations. NMR studies show that photochemically generated 1 O2 oxidizes all but one of these acenes to the corresponding endoperoxides in organic solvent. The rates of these oxidations correlate with the number and types of fused arenes, with longer dialkoxyacenes generally oxidizing faster than shorter derivatives. Finally, irradiation of these acenes in acidic, oxidizing environments cleaves the ether bonds. This work impacts those working in organic optoelectronics, as well as those interested in harnessing photogenerated reactive oxygen species in functional materials.

Combining Top-Down and Bottom-Up with Photodegradable Layer-by-Layer Films.

Layer-by-layer (LbL) self-assembly of polymer coatings is a bottom-up fabrication technique with broad applicability across a wide range of materials and applications that require control over interfacial properties. While most LbL coatings are chemically uniform in directions both tangent and perpendicular to their substrate, control over the properties of surface coatings as a function of space can enhance their function. To contribute to this rapidly advancing field, our group has focused on the top-down spatiotemporal control possible with photochemically reactive LbL coatings, harnessed through charge-shifting polyelectrolytes enabled by photocleavable ester pendants. The photolysis of the photocleavable esters degrades LbL films containing these polyelectrolytes. The chemical structures of the photocleavable groups dictate the wavelengths responsible for disrupting these coatings, ranging from ultraviolet to near-infrared in our work. In addition, spatially segregating reactive groups into "compartments" within LbL films has enabled us to fabricate reactive free-standing polymer films and multiheight photopatterned coatings. Overall, by combining bottom-up and top-down approaches, photoreactive LbL films enable precise control over the interfacial properties of polymer and composite coatings.

Small Changes With Big Consequences: Swapping Two Atoms In Side Chains Changes Phenylene-Ethynylene Packing And Fluorescence.

Engineering the properties of conjugated materials in the solid state is an unsolved, ongoing challenge important to fundamental understanding of how non-covalent interactions dictate packing and key properties, as well as the development of technologies based in organic optoelectronics. The most common design paradigm of such materials divide them into a "main chain" with extended conjugation, the chemical structure of which determines optoelectronic properties, and "side chains" not conjugated to the backbone, which provide solubility when they are long alkyl chains. This paper describes comparisons between phenylene-ethynylene molecules in which slight changes to the structure of "side chains"-swapping hydrogen and fluorine atomic position on an aromatic ring-results in unexpectedly large changes in the solid-state optical properties. In a pair of anisyl-terminated three-ring phenylene-ethynylenes, switching the side chain arenes of benzyl esters from 2,4,6-trifluoro to 2,3,6-trifluoro results in a shift in fluorescence emission spectra of over 100 nm, as well as the opposite direction of force-induced shifting of emission. Through a combination X-ray crystal structures, electronic structure calculations, and comparisons with other derivatives, we describe how the 2,4,6-trifluorinated side chains yield cofacial fluoroarene-arene stacking interactions that twist the PE backbone out of conjugation, while the 2,3,6-trifluoro side chains do not stack, instead yielding more coplanar PE backbones that form intermolecular aggregates. Overall, this work demonstrates how slight modifications to parts of conjugated materials normally considered ancillary to optoelectronic properties can determine their solid-state properties, epitomizing the challenge of rational design but at the same time offering opportunities for materials discovery and improved understanding of non-covalent interactions.

UV and NIR-Responsive Layer-by-Layer Films Containing 6-Bromo-7-hydroxycoumarin Photolabile Groups.

This paper describes polyelectrolyte multilayer films prepared by the layer-by-layer (LbL) technique capable of undergoing dissolution upon exposure to either ultraviolet or near-infrared light. Film dissolution is driven by photochemical deprotection of a random methacrylic copolymer with two types of side chains: (i) 6-bromo-7-hydroxycoumarinyl esters, photocleavable groups that are known to have substantial two-photon photolysis cross sections, and (ii) cationic residues from the commercially available monomer N,N-dimethylaminoethyl methacrylate (DMAEMA). In addition, the dependence of stability of both unirradiated and irradiated films on pH provides experimental evidence for the necessity of disrupting both ion-pairing and hydrophobic interactions between polyelectrolytes to realize film dissolution. This work therefore provides both new fundamental insight regarding photolabile LbL films and expands their applied capabilities to nonlinear photochemical processes.

Forcing Ladderenes into Plastic Semiconductors with Mechanochemistry.

May the force be with you: Xia, Burns, Martinez, and co-workers harnessed the ring strain of ladderenes to enable both their polymerization and mechanochemical unzipping to yield semiconducting polyacetylene-based block copolymers. These materials have promise as functional polymers for applications such as detection of physical stress.

Steric and Electronic Substituent Effects Influencing Regioselectivity of Tetracene Endoperoxidation.

This paper describes the influence of steric and electronic factors in the regioselectivity of endoperoxide formation of tetracene derivatives using (1)O2. A combination of kinetics experiments and product distributions resulting from these photosensitized oxidations demonstrates that, while the steric effect of o-alkyl groups on aryl substituents is highly localized to the substituted ring, the resistance to oxidation based on phenylethynyl substituents is more evenly distributed between the two reactive rings. These results are important for the rational design of highly persistent acenes.

Ullmann coupling mediated assembly of an electrically driven altitudinal molecular rotor.

Surface-bound molecular rotation can occur with the rotational axis either perpendicular (azimuthal) or parallel (altitudinal) to the surface. The majority of molecular rotor studies involve azimuthal rotors, whereas very few altitudinal rotors have been reported. In this work, altitudinal rotors are formed by means of coupling aryl halides through a surface-mediated Ullmann coupling reaction, producing a reaction state-dependent altitudinal molecular rotor/stator. All steps in the reaction on a Cu(111) surface are visualized by low-temperature scanning tunneling microscopy. The intermediate stage of the coupling reaction is a metal-organic complex consisting of two aryl groups attached to a single copper atom with the aryl rings angled away from the surface. This conformation leads to nearly unhindered rotational motion of ethyl groups at the para positions of the aryl rings. Rotational events of the ethyl group are both induced and quantified by electron tunneling current versus time measurements and are only observed for the intermediate structure of the Ullmann coupling reaction, not the starting material or finished product in which the ethyl groups are static. We perform an extensive set of inelastic electron tunneling driven rotation experiments that reveal that torsional motion around the ethyl group is stimulated by tunneling electrons in a one-electron process with an excitation energy threshold of 45 meV. This chemically tunable system offers an ideal platform for examining many fundamental aspects of the dynamics of chemically tunable molecular rotor and motors.

Combining electronic and steric effects for highly stable unsymmetric pentacenes.

This paper describes the reactivity of unsymmetrically substituted pentacenes to photochemical oxidation. Acenes in general, and pentacenes in particular, are a key family of compounds for a variety of organic electronics applications. The instability of many pentacene derivatives, particularly to oxidation, is an important restriction in their applicability. Several substitution strategies for decreasing the reactivity of pentacene exist, but these almost always involve symmetrically substituted derivatives, restricting the chemical space of structures from which to choose. In this paper, we demonstrate that combining electronic and steric effects yields highly stable unsymmetrically substituted pentacenes.

Electronic effects of ring fusion and alkyne substitution on acene properties and reactivity.

This paper describes the synthesis and systematic study of substituted acenes that have differences in conjugation both along their long axes (by the number of fused benzene or thiophene rings) and along their short axes (by the number of arylethynyl substituents). These acenes include what we believe to be the first reported examples of five new subclasses of substituted acenes. Systematic analyses of data obtained using absorbance and fluorescence spectroscopies, cyclic voltammetry, and DFT calculations reveal clear correlations between these common structural perturbations to acene structure and the key parameters, such as HOMO-LUMO gap, frontier molecular orbital energies, and reactivity with singlet oxygen.

Mechanism of the hydrophobic effect in the biomolecular recognition of arylsulfonamides by carbonic anhydrase.

The hydrophobic effect--a rationalization of the insolubility of nonpolar molecules in water--is centrally important to biomolecular recognition. Despite extensive research devoted to the hydrophobic effect, its molecular mechanisms remain controversial, and there are still no reliably predictive models for its role in protein-ligand binding. Here we describe a particularly well-defined system of protein and ligands--carbonic anhydrase and a series of structurally homologous heterocyclic aromatic sulfonamides--that we use to characterize hydrophobic interactions thermodynamically and structurally. In binding to this structurally rigid protein, a set of ligands (also defined to be structurally rigid) shows the expected gain in binding free energy as hydrophobic surface area is added. Isothermal titration calorimetry demonstrates that enthalpy determines these increases in binding affinity, and that changes in the heat capacity of binding are negative. X-ray crystallography and molecular dynamics simulations are compatible with the proposal that the differences in binding between the homologous ligands stem from changes in the number and organization of water molecules localized in the active site in the bound complexes, rather than (or perhaps in addition to) release of structured water from the apposed hydrophobic surfaces. These results support the hypothesis that structured water molecules--including both the molecules of water displaced by the ligands and those reorganized upon ligand binding--determine the thermodynamics of binding of these ligands at the active site of the protein. Hydrophobic effects in various contexts have different structural and thermodynamic origins, although all may be manifestations of the differences in characteristics of bulk water and water close to hydrophobic surfaces.

Photoresponsive gels prepared by ring-opening metathesis polymerization.

This communication describes photoresponsive gels, prepared using ring-opening metathesis polymerization (ROMP), that dissolve upon irradiation with ultraviolet light. Exposure of mixtures of norbornene-type ROMP monomers and new photoreactive cross-linkers comprising two norbornene units bound through a chain containing o-nitrobenzyl esters (NBEs) to well-known ruthenium carbene catalysts gave cross-linked polymer networks that swelled in organic solvents or water depending on the structure of the monomer. These gels became homogeneous upon irradiation with UV light, consistent with breaking of the cross-links through photolysis of the NBE groups. The irradiation time required for homogenization of the gels depended on the cross-link density and the structure of the photoresponsive cross-linker.

Infochemistry and infofuses for the chemical storage and transmission of coded information.

This article describes a self-powered system that uses chemical reactions--the thermal excitation of alkali metals--to transmit coded alphanumeric information. The transmitter (an "infofuse") is a strip of the flammable polymer nitrocellulose patterned with alkali metal ions; this pattern encodes the information. The wavelengths of 2 consecutive pulses of light represent each alphanumeric character. While burning, infofuses transmit a sequence of pulses (at 5-20 Hz) of atomic emission that correspond to the sequence of metallic salts (and therefore to the encoded information). This system combines information technology and chemical reactions into a new area--"infochemistry"--that is the first step toward systems that combine sensing and transduction of chemical signals with multicolor transmission of alphanumeric information.

Substituent Effect in Pyridinium Alkynylanthracenes on their Performance as Photosensitizers for Photodynamic Therapy.

Progress in photodynamic therapy (PDT) relies on the design and synthesis of photosensitizers that can efficiently sensitize singlet oxygen using visible light irradiation while displaying limited dark toxicity. Here, we highlight the paper by Linker and coworkers published in this issue of Photochemistry and Photobiology, which evaluates the effect of the regiochemistry of pyridinium rings in three isomeric pyridinium alkynylanthracenes on their performance as photosensitizers for PDT in HeLa cells.

Red-Emitting, Acene-Doped Conjugated Polymer Nanoparticles that Respond Ratiometrically to Photogenerated 1O2.

Fluorophores that respond to external stimuli on demand have numerous applications in imaging and chemical or biological sensing. In this paper, we describe conjugated polymer nanoparticles (CPNs) that comprise a donor polymer matrix and a red-fluorescent, singlet oxygen-reactive heteroacene dopant (DE-TMT) that display a ratiometric response upon photo-oxidation. This ratiometric response can be tuned by the level of doping of DE-TMT, the identity of the conjugated polymer matrix used, and the blending of two conjugated polymers together to access red-shifted emission wavelengths. We followed a rational design process that combined (i) fundamental understanding of the influence of the chemical structure on luminescence spectra and efficiencies, energy transfer efficiencies, and reactivity and (ii) systematically determining how blending multiple chromophores in nanoparticles influences energy transfer efficiencies and the speed of optical responses to irradiation. Our approach of refining the compositions of these nanoparticles has yielded materials that combine many desirable characteristics for analytical applications-utility in aqueous environments, high quantum yield, emission of red light, and ratiometric luminescent responses. We anticipate that the type of approach described herein can be of use to others in designing CPNs for luminescence applications.

Parallel scanning-optical nanoscopy with optically confined probes.

We report the imaging of sub-diffraction limited features using an optical probe generated by focusing a round spot at one wavelength, lambda(1) = 405 nm, and a ring-shaped spot at a second wavelength, lambda(2) = 532 nm, onto a thin photochromic layer that coats the nanostructures. Illumination at lambda(2) turns the photochromic layer opaque to lambda(1) everywhere except at the centre of the ring, where the illumination at lambda(1) penetrates and probes the underlying nanostructure. We confirm that this optically confined probe increases image contrast and is able to resolve features smaller than the far-field diffraction limit. Furthermore, by using an array of dual-wavelength diffractive microlenses, we demonstrate the feasibility of parallelizing this approach. Compared to previous approaches, our technique is not limited to fluorescence imaging.

Turning on solid-state phosphorescence of platinum acetylides with aromatic stacking.

Neat solids that phosphoresce under ambient conditions are rare due to aggregation-caused quenching. This communication describes a platinum acetylide (PtPE) that phosphoresces as a solid due to programmed aromatic stacking interactions of pendant groups that prevent intermolecular aggregation.

Infochemistry: encoding information as optical pulses using droplets in a microfluidic device.

This article describes a new procedure for generating and transmitting a message--a sequence of optical pulses--by aligning a mask (an opaque sheet containing transparent "windows") below a microfluidic channel in which flows an opaque continuous fluid containing transparent droplets. The optical mask encodes the message as a unique sequence of windows that can transmit or block light; the flow of transparent droplets in the channel converts this message into a sequence of optical pulses. The properties of the windows on the mask (e.g., their size, wavelength of transmittance, orientation of polarization) determine the information carried in these optical pulses (e.g., intensity, color, polarization). The structure of a transmitted signal depends on the number and spacing of droplets in the channel. Fourier transformation can deconvolve superimposed signals created by the flow of multiple droplets into the message that a single droplet would transmit. The research described in this contribution explores a new field at the intersection of chemistry, materials science, and information technology: infochemistry.