Synthesis and Properties of Benzo-Fused Indeno[2,1-c]fluorenes.

A set of fully-conjugated indenofluorenes has been synthesized and confirmed by solid-state structure analysis. The indeno[2,1-c]fluorenes and their benzo-fused analogues all contain the antiaromatic as-indacene core. The molecules possess high electron affinities and show a broad absorption that reaches into the near-IR region of the electromagnetic spectrum. All of the featured compounds reversibly accept up to two electrons as revealed by cyclic voltammetry. Analysis of molecule tropicity using NICS-XY scan calculations shows that, while the as-indacene core is less paratropic than s-indacene, benz[a]-annulation further reduces the antiaromaticity of the core. Antiaromatic strength of the as-indacene core can also be tuned by the position of fusion of additional arenes on the outer rings.

Harnessing solid-state packing for selective detection of chloride in a macrocyclic anionophore.

We report the synthesis of an inherently fluorescent macrocyclic receptor for chloride. The use of a disulphide tether provides for an excellent yield in the macrocyclization step. This compound binds chloride in the solution and solid state, and while unstable over time in aqueous solution, shows a selective response toward chloride over other anions in the solid state due to intermolecular interactions between fluorophore backbones. Surprisingly, the optoelectronic response to anions differs in solution and the films, with a distinct colorimetric response observed only in the film.

Solid-State Examination of Conformationally Diverse Sulfonamide Receptors Based on Bis(2-anilinoethynyl)pyridine, -Bipyridine, and -Thiophene.

Utilizing an induced-fit model and taking advantage of rotatable acetylenic C(sp)-C(sp2) bonds, we disclose the synthesis and solid-state structures of a series of conformationally diverse bis-sulfonamide arylethynyl receptors using either pyridine, 2,2'-bipyridine, or thiophene as the core aryl group. Whereas the bipyridine and thiophene structures do not appear to bind guests in the solid state, the pyridine receptors form 2 + 2 dimers with water molecules, two halides, or one of each, depending on the protonation state of the pyridine nitrogen atom. Isolation of a related bis-sulfonimide derivative demonstrates the importance of the sulfonamide N-H hydrogen bonds in dimer formation. The pyridine receptors form monomeric structures with larger guests such as BF4- or HSO4-, where the sulfonamide arms rotate to the side opposite the pyridine N atom.

Facile Synthesis and Properties of 2-λ(5)-Phosphaquinolines and 2-λ(5)-Phosphaquinolin-2-ones.

Treatment of 2-ethynylanilines with P(OPh)3 gives either 2,2-diphenoxy-2-λ(5)-phosphaquinolines or 2-phenoxy-2-λ(5)-phosphaquinolin-2-ones under transition-metal-free conditions. This reaction offers access to an underexplored heterocycle, which opens up the study of the fundamental nature of the N=P(V) double bond and its potential for delocalization within a cyclic π-electron system. This heterocycle can serve as a carbostyril mimic, with application as a bioisostere for pharmaceuticals based on the 2-quinolinone scaffold. It also holds promise as a new fluorophore, since initial screening reveals quantum yields upwards of 40%, Stokes shifts of 50-150 nm, and emission wavelengths of 380-540 nm. The phosphaquinolin-2-ones possess one of the strongest solution-state dimerization constants for a D-A system (130 M(-1)) owing to the close proximity of a strong acceptor (P=O) and a strong donor (phosphonamidate N-H), which suggests that they might hold promise as new hydrogen-bonding hosts for optoelectronic sensing.

Ion and molecular recognition using aryl-ethynyl scaffolding.

The aryl-ethynyl linkage has been extensively employed in the construction of hosts for a variety of guests. Uses range from ion detection (e.g., of metal cations in the environment or industrial waste and of anions prevalent in nature), to molecular mimics for biological systems, and to applications targeting future safety issues (such as CO2 capture and indicators for the manufacture of chemical weapons). This Focus Review examines the utilization of the aryl-ethynyl linkage in engineering host molecules for a variety of different guests, and how the alkyne unit plays an integral part as both a rigid scaffolding section in host geometry design as well as a linker to allow conjugative communication between discrete π-electron systems.

Scalable synthesis of 5,11-diethynylated indeno[1,2-b]fluorene-6,12-diones and exploration of their solid state packing.

We report a new synthetic route to 5,11-disubstituted indeno[1,2-b]fluorene-6,12-diones that is amenable to larger scale reactions, allowing for the preparation of gram amounts of material. With this new methodology, we explored the effects on crystal packing morphology for the indeno[1,2-b]fluorene-6,12-diones by varying the substituents on the silylethynyl groups.

Synthesis and solid-state structures of a macrocyclic receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold.

A fluorescent macrocyclic anion receptor based on the 2,6-bis(2-anilinoethynyl)pyridine scaffold has been synthesized to investigate the mechanism of fluorescence quenching in this class of compounds. X-ray crystallography reveals that the binding pocket of the receptor is a natural host to both H2O and HCl, accommodating either molecule in nearly identical environments. Our studies show that protonation, not collisional quenching, is responsible for the observed fluorescence quenching response.

Synthesis and Properties of Fully-Conjugated Indacenedithiophenes.

The synthesis and characterization of four fully-conjugated indacenedithiophenes (IDTs) are disclosed. In contrast to anthradithiophenes, regioselective synthesis of both syn and anti isomers is readily achieved. Thiophene fusion imparts increased paratropic character on the central indacene core as predicted by DFT calculations and confirmed by 1H NMR spectroscopy. IDTs exhibit red-shifted absorbance maxima with respect to their all-carbon analogues and undergo two-electron reduction and one-electron oxidation.

Indeno[2,1-c]fluorene: a new electron-accepting scaffold for organic electronics.

A new class of fully conjugated indenofluorenes has been synthesized and confirmed by solid-state structure analysis. These indeno[2,1-c]fluorene molecules, containing an antiaromatic as-indacene core (in red), possess high electron affinities and show a broad absorption that reaches into the near-IR region of the electromagnetic spectrum. All of the featured compounds reversibly accept up to two electrons. Their electronic properties make this class of compounds attractive for applications in organic electronic devices.

Diazaheterocycle analogues of tetracene: synthesis and properties of a naphtho-fused cinnoline and a naphtho-fused isoindazole.

The synthesis and characterization of a diethynyl naphtho-fused cinnoline and isoindazole are described. The results show that both electron-accepting and electron-donating molecules can be prepared from a common intermediate.

Fluoreno[4,3-c]fluorene: a closed-shell, fully conjugated hydrocarbon.

The synthesis and optoelectronic properties of 24 π-electron, formally antiaromatic 4,11-di-t-butyl-1,8-dimesitylfluoreno[4,3-c]fluorene (FF) are presented. The solid-state structure shows that the outer rings are aromatic, while the central four rings possess a bond-localized 2,6-naphthoquinone dimethide motif (in red). The biradical character of FF is assessed experimentally and computationally; the results of which implicate a closed-shell ground state.

Ionic Stabilization of the Polythiophene-Oxygen Charge-Transfer Complex.

A substantial reduction in the rate of irreversible polymer photo-oxidation was observed through the ionic stabilization of the polymer-O2 charge-transfer complex (CTC) in amorphous polythiophene thin films. Through the incorporation of anionic functionality containing mobile cations, it was found that CTC stability increases with increasing cation charge density. This results in an increased rate of electron transfer to molecular oxygen relative to photosensitization and reaction of 1O2, leading to a reduction in the overall rate of polymer degradation. UV-vis and FTIR spectroscopy were utilized to determine the identity of intermediate and irreversible photodegradation products as well as the effect of ion identity on the dominant photo-oxidation mechanism. As polymer-O2 CTCs are common in the photo-oxidation of many conjugated polymers, these results have significant implications for the ongoing effort to produce commercially viable organic electronic and photonic devices.