The design, synthesis and photophysical properties of a Low Molecular Weight pH-responsive Gelator (LMWG) based on alkoxy group functionalized DCDHF-Hydrazones (DCDHF-H) are described. A straightforward synthesis of DCDHF-Hydrazone (DCDHF-H) chromophores was achieved via simple azo-coupling starting from 2-(dicyanomethylene)-2,5-dihydro-4,5,5trimethylfuran-3-carbonitrile and alkoxy bearing aryl diazonium chloride derivatives. The DCDHF-H efficiently gelate selected organic solvents and reversibly respond to pH stimuli with a gel-sol conversion and an associated color change from yellow to purple. Self-assembly of these molecules, as indicated by X-ray crystallography, occurs via cooperative π-π stacking and van der Waals interactions producing gelation in some pure and mixed organic solvents.Furthermore, the presence of acidic or alkaline gases leads to a dramatic change in the rheological properties with potential applications in areas such as gas detection devices and drug release systems. Scanning electron microscopy (SEM) and transmission electron Page | 2 microscopy (TEM) studies of the xerogels obtained from n-propanol provide visual images revealing the formation of fibrous nanostructures.

Nanostructures fabricated from multi-stimuli responsive DCDHF-hydrazone molecular switches to function as colorimetric reversible gas probes.

A series of 1,3-diphenyl-6-alkyl/arylfulvenes was prepared, and the electrochemical properties were investigated. The addition of phenyl groups about the fulvene raised the reduction potential and helped to stabilize the electrochemically generated radical anion. The addition of various functional groups onto the phenyl ring at the 6-position of 1,3,6-triphenylfulvene results in a linear free energy relationship between reduction potential and the Hammett substituent constant, σ. Further extending the conjugation at the 6-position of 1,3-diphenyl-6-arylfulvenes increases the reversibility of the redox reactions, but does not appear to further stabilize the generated radical anion. This in-depth investigation provides evidence that the compounds studied may have utility in light-harvesting applications.

The reagent 4‐(pentafluorosulfanyl)benzenediazonium tetrafluoroborate (1) was synthesized and isolated as a stable salt for the first time; its application in a wide assortment of transformations was subsequently investigated. A series of novel SF5‐bearing alkenes, alkynes, and biaryl derivatives were synthesized by employing Heck–Matsuda, Sonogashira, and Suzuki coupling protocols. Dediazoniation with TMSX (X = Hal; N3; and CN) and NH4SCN in [BMIM][BF4] as solvent furnished the corresponding p‐SF5–C6H4X derivatives. The azide derivative p‐SF5–C6H4N3 entered into click chemistry with phenylacetylenes to furnish the corresponding triazoles. The 4,4′‐bis(pentafluorosulfanyl)biphenyl was synthesized by homo‐coupling using Pd(OAc)2. The corresponding azo compounds were obtained through azo‐coupling with reactive aromatic nucleophiles (1,3‐dimethoxybenzene, 1,3,5‐trimethoxybenzene, 1,2,4‐trimethoxybenzene, aniline and phenol). Fluorodediazoniation in [BMIM][PF6] and [BMIM][BF4] selectively furnished the fluoro derivative p‐SF5–C6H4F. Dediazoniation in [BMIM][NTf2] gave p‐SF5–C6H4OS(O)(CF3)=NSO2CF3 as the major and p‐SF5–C6H4‐NTf2 as the minor products. Homolytic dediazoniation in MeCN/NaI gave the unsymmetrical biaryls p‐SF5–C6H4‐Ar (ArH = mesitylene and p‐xylene) along with p‐SF5–C6H4I. Analysis of the dediazoniation product mixtures indicated that dediazoniation of p‐SF5–C6H4N2+ BF4– in low nucleophilicity, highly ionizing, solvents (TfOH, TFE, HFIP, TFAH) is mainly heterolytic, while in MeOH it is mainly homolytic. The isodesmic reaction p‐SF5–C6H4+ + R‐C6H5 → SF5–C6H5 + p‐R‐C6H4+ (with R = NO2, CF3, H) was gauged by DFT at various levels and by PCM.