Wenji Wang

Reversible luminescence color switching in the crystal polymorphs of 2,7-bis(2′-methyl-[1,1′-biphenyl]-4-yl)-fluorenone by thermal and mechanical stimuli

Smart organic luminescence materials that exhibit a reversible stimuli-responsive change of luminescence color in the solid state without changing the chemical structure of their component molecules have attracted increasing interest. We employed the design strategy of introducing different weak interactions into the same molecular system to synthesize 2,7-bis(2′-methyl-[1,1′-biphenyl]-4-yl)-fluorenone (MPF). Two crystal polymorphs of MPF, green-yellow crystal G-MPF and orange crystal O-MPF, were obtained through culturing the single crystal under the different crystallization conditions of diffusing diethyl ether into its respective tetrahydrofuran or CH2Cl2 solution. Both of the two crystal polymorphs exhibit high luminous efficiency and reversible stimuli-responsive solid-state luminescence color switching. Upon heating the green crystal G-MPF or grinding the orange crystal O-MPF, their emission reversibly changes between green at 530 nm and orange at 570 nm. The X-ray single-crystal structures, characterization of the photophysical properties, powder X-ray diffraction and differential scanning calorimetry provide insight into the phase transformation and the luminescence behavior. The results indicate that the green emission of G-MPF originates from molecular J-aggregation and the orange emission of O-MPF originates from static excimers. This work discusses the relationship between the molecular stacking mode and the photophysical properties, and demonstrates a molecular design strategy to obtain stimuli-responsive organic solid-state luminescence switching materials.

A dual functional probe: sensitive fluorescence response to H2S and colorimetric detection for SO32−

Hydrogen sulfide (H2S) and sulfite (SO32−) are two important sulfur-containing species that play different and important roles in industrial and biological processes. Accordingly, the development of efficient methods for simple, rapid, sensitive and selective monitoring of H2S and SO32− is of the utmost importance in both environmental and biological sciences. In this study, we developed a new dual functional probe NIR-DNP for discriminative detection of H2S and SO32−. This probe can sense H2S and SO32− via two different approaches, a significant near-infrared fluorescence enhancement and color change from purple to cyan induced by H2S as well as a visible color change from purple to colorless caused by SO32−. The detection limits of the probe NIR-DNP for H2S and SO32− in aqueous solutions were 36.53 nM and 33.33 nM, respectively. Competitive experiments demonstrated that the probe NIR-DNP had a high fluorescence selectivity for H2S and excellent colorimetric selectivity for SO32− over other analytes. The sensing mechanism of the probe toward H2S and SO32− was based on the H2S-induced thiolysis of dinitrophenyl ether and SO32−-induced nucleophilic addition, respectively. Further investigation showed that the probe NIR-DNP could be used to develop an easy-to-prepare and easy-to-detect paper-based test strip for cheap and effective detection of SO32−. Also, the probe NIR-DNP has the potential to image exogenous and endogenous H2S in living cells.

Thiophene-functionalized octupolar triindoles: Synthesis and photophysical properties

Two thiophene-functionalized octupolar triindole molecules were synthesized through Suzuki and Sonogashira cross-coupling reactions. Their photophysical and electrochemical properties were explored. The spectroscopic data demonstrate that triindole is an excellent rich electronic central donor for building octupolar optoelectronic molecules and possesses excellent luminescent properties. Thiophenylethynyl substituted triindole compound 3,8,13-tri(2-thiophenylethynyl)-5,10,15-tributyltriindole forms an intermolecular aggregation induced by π-π stacking from the rigid coplanar molecular scaffold. The redox curves and results of theoretical calculation imply that the two compounds have low ionization potential and low E(1/2 oxd), which may be originated from the high electronic density of both triindole and thiophene groups.

Symmetric and unsymmetric thienyl-substituted fluorenone dyes: static excimer-induced emission enhancement

In this work, we designed and synthesized four symmetric and asymmetric thienyl-substituted fluorenone compounds, which all exhibited typical AIE properties. Besides a high solid-state fluorescence quantum yield, the enhanced luminescence of their solid-state powders showed a 170 nm red-shift (from 380 to 550 nm) in comparison with the luminescence of their dilute tetrahydrofuran solutions. The photophysical properties and single-crystal structure, combined with the theoretical calculation, revealed that the bathochromic luminescence is due to the formation of static excimers.

Branched truxene and triindole compounds and their solid-state luminescent enhancement

C3-symmetric truxene and triindole have been widely used to design the branched optoelectronic molecules. However, most of them exhibit high luminous efficiency in the solution and quenched luminescence in the solid state. Here, we respectively chose alkylated truxene and triindole as the central core, 2-methylphenyl as the peripheral functional groups to synthesize three branched compounds. Their photophysical properties have been explored combining with the theoretical calculation. The three compounds exhibit good solubility and high solid-state fluorescence quantum yields. The absorption and emission peaks of triindole compound exhibit apparent red-shift in comparison with those of truxene compounds, which indicates triindole more highly electron delocalization than truxene. The single-crystal structure shows that alkylation of the central core and branched steric bulkiness of these molecules effectively reduce the intermolecular π⋯π stacking and avoid the non-radiative transition of these molecules from excited state to ground state in the solid state.

Frontispiece: Di-(2-picolyl)-N-(2-quinolinylmethyl)amine-Functionalized Triarylboron: Lewis Acidity Enhancement and Fluorogenic Discrimination Between Fluoride and Cyanide in Aqueous Solution

Triarylboron-based Lewis acids as fluoride sensors face a stimulating academic challenge because of the high hydration enthalpy of fluoride, and are usually influenced by a competing response for cyanide ion. Herein, we present a new triarylborane functionalized by a metal-ion ligand, di-(2-picolyl)-N-(2-quinolinylmethyl)amine, with subsequent metalation. In aqueous solution, this triarylborane (QB) can capture fluoride and cyanide anions through chelation induced by the synergy of boron and metal ions. Moreover, this triarylborane moiety acts as a fluorescent reporter of the binding, allowing for discrimination between fluoride and cyanide anions through dual-channel fluorescence changes. The different chelation models and fluorogenic responses of this sensor toward F- and CN- were verified by the single-crystal structures of 2-to-2 adduct for KCN and 1-to-1 for KF.