Yuming Zhao

Ultrafast optical Kerr effect measurements of third-order nonlinearities in cross-conjugated iso-polydiacetylene oligomers

We present a study on the ultrafast third-order nonlinearities of a novel series of iso-polydiacetylene oligomers (iso-PDAs). Unlike polydiacetylenes that contain a linearly-conjugated backbone, iso-PDAs have a backbone that is cross-conjugated. A new Kerr-gate technique, differential optical Kerr effect (DOKE) detection, is used to measure third-order nonlinear susceptibilities, χ(3), and second hyperpolarizabilities, γ, of monomer, dimer, trimer, pentamer, and heptamer samples in tetrahydrofuran (THF) solutions. A linear increase in γ as a function of the number of repeat units is observed for all samples except the monomer, suggesting that the fixed-length linearly conjugated segments dominate the electronic polarizability. An added increase to the oligomer nonlinearities due to communication along the cross-conjugated path is not observed. The largest nonlinearity was observed in the heptamer sample, displaying a second hyperpolarizability relative to the THF solvent of γheptamer/γTHF=181±9. In additi...

Selective and reversible noncovalent functionalization of single-walled carbon nanotubes by a pH-responsive vinylogous tetrathiafulvalene-fluorene copolymer.

A vinylogous tetrathiafulvalene (TTFV) monomer was prepared and copolymerized with fluorene to give a conformationally switchable conjugated copolymer. This copolymer was shown to undergo a conformational change upon protonation with trifluoroacetic acid (TFA). When mixed with single-walled carbon nanotubes (SWNTs), this TTFV-fluorene copolymer exhibited strong interactions with the SWNT surface, leading to stable, concentrated nanotube dispersions in toluene. Photoluminescence excitation mapping indicated that the copolymer selectively disperses low-diameter SWNTs, as would be expected from its ability to form a tightly coiled conformation on the nanotube surface. Addition of TFA to the copolymer-SWNT dispersion resulted in a rapid conformational change and desorption of the polymer from the SWNT surface, resulting in precipitation of pure SWNTs that were completely free of polymer. Importantly, the nanotubes isolated after dispersion and release by the TTFV-fluorene copolymer were more pure than the original SWNTs that were initially dispersed.

Reversible dispersion and releasing of single-walled carbon nanotubes by a stimuli-responsive TTFV-phenylacetylene polymer

A TTFV-phenylacetylene folding polymer was synthesized to exhibit the property of reversibly dispersing and releasing single-walled carbon nanotubes in organic solvents under the control of redox or pH stimuli.

Synthesis and properties of conjugated oligoyne-centered π-extended tetrathiafulvalene analogues and related macromolecular systems.

Alkynyl-substituted phenyldithiafulvenes have been found to act as versatile building blocks for the construction of π-conjugated molecular rods, shape-persistent macrocycles (SPMs), and conducting polymers. Through Cu(I)-catalyzed alkynyl homocoupling, a series of linear-shaped π-extended tetrathiafulvalene analogues (exTTFs) carrying conjugated oligoynes (ranging from diyne to hexayne) as the central π-bridge were readily prepared. The solid-state properties and reactivities of diyne- and tetrayne-centered exTTFs were characterized by X-ray crystallography and differential scanning calorimetry (DSC), while the electronic properties of the oligoyne-exTTFs were elucidated by UV-vis absorption spectroscopy and density functional theory (DFT) calculations. Cyclic voltammetric analysis showed that the terminal phenyldithiafulvene groups of the oligyne-exTTFs could undergo oxidative coupling to form tetrathiafulvalene vinylogue (TTFV)-linked polymer wires. Through a different synthetic route involving oxidative dimerization and Pd/Cu-catalyzed alkynyl homocoupling, the acetylenic phenyldithiafulvene precursors led to shape-persistent macrocycles where the formation of trimeric macrocycles was particularly favored due to the small ring strain incurred. Finally, spectroelectrochemical studies on these oligoyne and TTF hybrid materials disclosed electrochromic and molecular redox-controlled switching properties applicable to molecular electronic and optoelectronic devices.

1,8-Pyrenylene−Ethynylene Macrocycles

A concise, highly regioselective synthesis of 1,8-dibromo-4,5-dialkoxypyrenes has been developed and exploited in the synthesis of some 1,8-pyrenylene-ethynylene macrocycles. The (1)H NMR data and NICS calculations indicate that there is little or no macrocyclic ring current. Concentration-dependent UV-visible studies indicate no aggregation at low concentration, but 8b forms dimers with voids suitable for intercalation of small molecules in the solid state.

Highly π-Extended TTF Analogues with a Conjugated Macrocyclic Enyne Core

The synthesis of a class of highly pi-extended tetrathiafulvalene derivatives (1a and 1b) was explored using Sonogashira macrocyclization as a key step. The solid-state structure of 1b was characterized by X-ray single crystallography, showing a substantially bent, S-shaped molecular backbone and an ordered packing geometry in a pi-alkyl-alkyl-pi stacking fashion. Electronic and redox properties of 1b were investigated by UV-vis absorption, fluorescence spectroscopy, and cyclic voltammetry.

Acetylenic Phenyldithiafulvene: A Versatile Synthon for TTFV-Based Macromolecules

An acetylenic phenyldithiafulvene was developed as a versatile synthon for diverse TTFV-based macromolecular scaffolds. Through different coupling reaction sequences, shape-persistent macrocycles and linear TTFV-embedded polymers have been obtained and thereafter characterized by spectroscopic and voltammetric analyses. The TTFV polymer thin films generated via electropolymerization of a dithiafulvenyl-end-capped diyne monomer showed promising prospects in electrochromic and redox switchable molecular devices.

H-shaped OPE/OPV oligomers: a new member of 2D-conjugated fluorophore cores.

A new class of two-dimensional (2D), pi-conjugated, skewed H-shaped co-oligomers of phenylene vinylene and phenylene ethynylene (11a- d, termed H-mers) were synthesized using Sonogashira coupling and Wittig-Horner reactions as the key steps. Electronic and spectroscopic properties of the H-mers were investigated by UV-vis absorption, fluorescence spectroscopic techniques, and ab initio calculations (HF/3-21G). Two amino-containing functional H-mers (11b and 11d) were found to exhibit appealing fluorescence sensitivity to selected Brønsted acids and transition-metal ions.

Tetrathiafulvalene vinylogues as versatile building blocks for new organic materials

Although tetrathiafulvalene (TTF) and its derivatives have been extensively studied as important organic electronic materials over the past half century, tetrathiafulvalene vinyl-ogues (TTFVs) still remain a relatively underdeveloped branch in the family of TTF derivatives. Our recent work has investigated the synthesis and characterization of a class of diphenyl-substituted TTFVs carrying alkynyl functionality. The unique conformational and redox properties of such TTFV derivatives along with the versatile chemistry enabled by acetylenic groups (e.g., metal-catalyzed coupling and click reactions) have led us to a variety of functional molecular architectures ranging from oligoynes, polymers, and molecular tweezers, to macrocycles. Property studies of these new TTFV-based molecular materials point to appealing applications in molecular electronics and optoelectronics.

Biscrown-annulated TTFAQ-dianthracene hybrid: synthesis, structure, and metal ion sensing.

A new fluorescence chemosensor (3) made up of a biscrown-annulated TTFAQ receptor and two anthracene fluorophores was designed and synthesized. Its solid-state structure was disclosed by X-ray crystallographic analysis, while fluorescence titrations indicated a high sensitivity for large hard metal cations such as Ba(2+).