Jung Su Park

Ion-Mediated Electron Transfer in a Supramolecular Donor-Acceptor Ensemble

Charging Back and Forth Ion binding by proteins can exert a major influence on electron transfer events in biological systems. Park et al. (p. 1324) discovered an analogous phenomenon in a simpler synthetic system. Specifically, a certain flexible molecule, known as a calix[4]pyrrole derivative, adopts a conical conformation upon binding anions, such as chloride or bromide, and this in turn leads to electron transfer to a guest acceptor that drifts into the cone. Addition of a cation that fitted more snugly into the conical cavity resulted in a reversal of the electron transfer reaction. The whole process was mapped out by spectroscopic and crystallographic characterization of the intermediates and products. Electron transfers in a weakly bound molecular complex are driven forward by anions and backward by cations. Ion binding often mediates electron transfer in biological systems as a cofactor strategy, either as a promoter or as an inhibitor. However, it has rarely, if ever, been exploited for that purpose in synthetic host-guest assemblies. We report here that strong binding of specific anions (chloride, bromide, and methylsulfate but not tetrafluoroborate or hexafluorophosphate) to a tetrathiafulvalene calix[4]pyrrole (TTF-C4P) donor enforces a host conformation that favors electron transfer to a bisimidazolium quinone (BIQ2+) guest acceptor. In contrast, the addition of a tetraethylammonium cation, which binds more effectively than the BIQ2+ guest in the TTF-C4P cavity, leads to back electron transfer, restoring the initial oxidation states of the donor and acceptor pair. The products of these processes were characterized via spectroscopy and x-ray crystallography.

Positive Homotropic Allosteric Receptors for Neutral Guests: Annulated Tetrathiafulvalene-Calix[4]pyrroles as Colorimetric Chemosensors for Nitroaromatic Explosives

The study of positive homotropic allosterism in supramolecular receptors is important for elucidating design strategies that can lead to increased sensitivity in various molecular recognition applications. In this work, the cooperative relationship between tetrathiafulvalene (TTF)-calix[4]pyrroles and several nitroaromatic guests is examined. The design and synthesis of new annulated TTF-calix[4]pyrrole receptors with the goal of rigidifying the system to accommodate better nitroaromatic guests is outlined. These new derivatives, which display significant improvement in terms of binding constants, also display a positive homotropic allosteric relationship, as borne out from the sigmoidal nature of the binding isotherms and analysis by using the Hill equation, Adair equation, and Scatchard plots. The host-guest complexes themselves have been characterized by single-crystal X-ray diffraction analyses and studied by means of UV-spectroscopic titrations. Investigations into the electronic nature of the receptors were made by using cyclic voltammetry; this revealed that the binding efficiency was not strictly related to the redox potential of the receptor. On the other hand, this work serves to illustrate how cooperative effects may be used to enhance the recognition ability of TTF-calix[4]pyrrole receptors. It has led to new allosteric systems that function as rudimentary colorimetric chemosensors for common nitroaromatic-based explosives, and which are effective even in the presence of potentially interfering anions.

Ion-Controlled On–Off Switch of Electron Transfer from Tetrathiafulvalene Calix[4]pyrroles to Li+@C60

Binding of chloride anion to a tetrathiafulvalene calix[4]pyrrole (TTF-C4P) donor results in ET to Li(+)@C(60) to produce the radical pair (TTF-C4P(•+)/Li(+)@C(60)(•-)), the structure of which was characterized by X-ray crystallographic analysis. The addition of tetraethylammonium cation, which binds more effectively than Li(+)@C(60)(•-) as a guest within the TTF-C4P cavity, leads to electron back-transfer, restoring the initial oxidation states of the donor and acceptor pair.

Selective-area and lateral epitaxial overgrowth of III–N materials by metal organic chemical vapor deposition

We describe the characteristics of single-crystal GaN regions obtained by selective-area and subsequent lateral epitaxial overgrowth using metal organic chemical vapor deposition. Under certain deposition conditions, the surface kinetics of the metal organic chemical vapor deposition process results in lateral growth of single-crystal GaN over the masked region. The lateral-to-vertical relative growth rate depends upon the orientation of stripe openings, the ratio of the “open” stripe width to the “masked” stripe width, and the growth conditions (e.g., temperature and V/III ratio). The specific orientations of the growth facets on the sidewalls of the laterally growing stripes are also dependent upon the growth conditions. The cathodoluminescence intensity of the GaN films indicate that improved materials are grown over the oxide mask.

Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles

The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix[4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix[4]pyrrole. The resulting polymeric materials, stabilized by combination of donor–acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1- and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of “smart” sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.

Tetrathiafulvalene diindolylquinoxaline: a dual signaling anion receptor with phosphate selectivity

Incorporation of tetrathiafulvalene into the backbone of a known neutral phosphate receptor, diindolylquinoxaline, yields a dual optical-electrochemical chemosensor for dihydrogen phosphate that functions in dichloromethane. This system shows selectivity for dihydrogen phosphate over other small anions and can be used to detect the presence of this analyte via fluorescence quenching or cyclic voltammetry.

Redox- and pH-Responsive Orthogonal Supramolecular Self-Assembly: An Ensemble Displaying Molecular Switching Characteristics

Two heteroditopic monomers, namely a thiopropyl-functionalized tetrathiafulvalene-annulated calix[4]pyrrole (SPr-TTF-C[4]P 1) and phenyl C61 butyric acid (PCBA 2), have been used to assemble a chemically and electrochemically responsive supramolecular ensemble. Addition of an organic base initiates self-assembly of the monomers via a molecular switching event. This results in the formation of materials that may be disaggregated via the addition of an organic acid or electrolysis.

Ion-Regulated Allosteric Binding of Fullerenes (C60 and C70) by Tetrathiafulvalene-Calix[4]pyrroles

The effect of ionic species on the binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV-vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F(-), Cl(-), and Br(-)) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host-guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host-guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators.

Properties of InGaN quantum-well heterostructures grown on sapphire by metalorganic chemical vapor deposition

We report the growth and characterization of InGaN heteroepitaxial thin films and quantum-well heterostructures on (0001) sapphire substrates. The III-N heteroepitaxial layers are grown by metalorganic chemical vapor deposition on sapphire substrates using various growth conditions. A comparison of the 300 K photoluminescence (PL) spectra of the samples indicates that a higher PL intensity is measured for the quantum-well structures having an intentional n-type Si-doping concentration. Furthermore, three-, five-, and eight-period InGaN quantum-well structures exhibit similar narrow PL spectra.

Selective-area and lateral epitaxial overgrowth of III-N materials by metalorganic chemical vapor deposition

Abstract We describe the characteristics of single-crystal GaN regions obtained by selective-area and subsequent lateral epitaxial overgrowth using metalorganic chemical vapor deposition. For a range of deposition conditions, the surface kinetics of the metalorganic chemical vapor deposition process results in an initial stage of selective-area growth, subsequently followed by the lateral growth of single-crystal GaN over the SiO 2 mask. The lateral-to-vertical relative growth rate depends upon the orientation of stripe openings with respect to the GaN crystal planes, the ratio of the “open” stripe width to the “masked” stripe width, and the specific growth conditions (e.g., temperature and V/III ratio). The crystalline orientations of the growth facets on the sidewalls of the laterally growing stripes are also dependent upon the growth conditions. The results of cathodoluminescence and transmission-electron microscopy studies of the GaN films indicate that materials with improved quality are grown over the oxide mask.