Long-range Through-space Charge Transfer in a pH-responsive Mixed Cyclophane of Pyridine and Teropyrene.

A large, strained (SE=44.2 kcal/mol) and conformationally flexible mixed cyclophane of pyridine and teropyrene was synthesized using two intramolecular Wurtz coupling reactions and an unprecedented Scholl reaction between the unreactive 2 positions of the pyrene systems in a triply bridged pyrenophane. Protonation of the pyridine unit results in a greatly enhanced preference for nesting in the cavity of the highly bent teropyrene system (θcalc =162.6°) and emergence of a charge transfer absorption band (λmax =592 nm) due to a long range (5.0-5.5 Å), through-space intramolecular transition between the teropyrene and pyridinium units, which does not exist in the neutral cyclophane.

Synthesis of anti-[1](1,6)Naphthaleno[1](1,6)naphthalenophane by Double Contractive Annulation of [2.2]Paracyclophane.

Two-directional contractive annulation of [2.2]paracyclophane has led to the synthesis of anti-[1](1,6)naphthaleno[1](1,6)naphthalenophane (3). This [1.1]cyclophane (SE = 56.6 kcal/mol) consists of two bent and twisted naphthalene units with interplanar distances as short as 2.74 Å. Despite the high strain and structural distortion, 3 was found to be unreactive toward potential cycloaddition partners (TCNE, DMAD) and under UV irradiation.

Carbon Quantum Dot-Incorporated Chitosan Hydrogel for Selective Sensing of Hg2+ Ions: Synthesis, Characterization, and Density Functional Theory Calculation.

A carbon quantum dot-based chitosan hydrogel was prepared in this work as a fluorescence sensor for the selective sensing of Hg2+ ions. Among the eight tested metal ions, the prepared hydrogel exhibited remarkable sensing selectivity and sensitivity toward Hg2+. The results demonstrated that a prominent fluorescence quenching at 450 nm was observed in the presence of Hg2+ with a linear response range of 0-100.0 nM and an estimated limit of detection of 9.07 nM. The as-prepared hydrogel demonstrates pH-dependent fluorescence intensity and sensitivity. The highest fluorescence intensity and sensitivity were obtained under pH 5.0. The excellent sensing selectivity could be attributed to a strong interaction between the hydrogel film and Hg2+ ions to form complexes, which provokes an effective electron transfer for fluorescence quenching. Results from density functional theory (DFT) calculation confirm that the interaction energies (ΔIE) of the hydrogel with three toxic metal ions (Hg2+, Cd2+, and Pb2+) are in the following order: Hg2+ > Cd2+ > Pb2+.

Synthesis of [2.2]Paracyclophane/9-Alkylfluorene Hybrids and the Discovery of a Solvent-assisted Rearrangement.

Work on the synthesis of [2.2]paracyclophane/9-alkylfluorene hybrids led to the discovery of the rearrangement of cyclopentadienone 7 to cyclophane 6. A DFT computational study revealed that this formal 1,3-alkyl shift occurs in two steps, but requires the participation of a solvent molecule (ethanol). The rearrangement could be avoided by generating 7 under mild conditions and using benzynes as dienophiles to afford the targeted cyclophanes 14 and 16, the latter of which exhibits dual fluorescence emission.

"Shadow" Synthesis, Structure, and Electronic Properties of [2.2](1,6)(1,8)Pyrenophane-1-monoene.

An unexpected side product of a McMurry reaction was found to be a new [2.2]pyrenophane consisting of two pyrene units with different substitution patterns as well as different types and degrees of distortion from planarity. The new pyrenophane exhibits both monomer and intramolecular excimer fluorescence. Natural bond orbital (NBO) analysis revealed that there is an intramolecular charge-transfer interaction from the more distorted pyrene system to the less distorted one. The origin of the new pyrenophane was traced back to an impurity that was present a full five steps prior to the McMurry reaction from which it was isolated. The pathway to the pyrenophane shadowed that of the main synthetic route.

Pyrenoimidazolyl-Benzaldehyde Fluorophores: Synthesis, Properties, and Sensing Function for Fluoride Anions.

Two structural isomers of (9H-pyreno[4,5-d]imidazol-10-yl)-benzaldehyde, with para and meta substitution patterns, were synthesized by condensation of 4,5-pyrenedione with terephthalaldehyde and isophthalaldehyde, respectively. These new pyrenoimidazole derivatives were characterized by single-crystal X-ray crystallography, UV-vis absorption spectroscopy, fluorescence spectroscopy, and cyclic voltammetry to elucidate their structural, solid-state packing, and electronic properties. Interactions of these compounds with fluoride anions in polar organic solvents (acetone and dimethyl sulfoxide) were investigated by NMR, UV-vis, and fluorescence techniques in conjunction with density functional theory calculations. UV-vis analysis showed that the binding of the two pyrenoimidazolyl benzaldehydes with fluoride anions resulted in significant colorimetric responses, while fluorescence studies showed that the para-pyrenoimidazolyl benzaldehyde behaved as an intramolecular charge transfer fluorescent probe, exhibiting ratiometric sensing performance to efficiently detect and quantify fluoride anions at the sub-millimolar level.