Jian-Zhen Liao

Multifunctional Radical-Doped Polyoxometalate-Based Host–Guest Material: Photochromism and Photocatalytic Activity

An effective strategy to synthesize multifunctional materials is the incorporation of functional organic moieties and metal oxide clusters via self-assembly. A rare multifunctional radical-doped zinc-based host-guest crystalline material was synthesized with a fast-responsive reversible ultraviolet visible light photochromism, photocontrolled tunable luminescence, and highly selective photocatalytic oxidation of benzylic alcohols as a result of blending of distinctively different functional components, naphthalenediimide tectons, and polyoxometalates (POMs). It is highly unique to link π-electron-deficient organic tectons and POMs by unusual POMs anion-π interactions, which are not only conducive to keeping the independence of each component but also effectively promoting the charge transfer or exchange among the components to realize the fast-responsive photochromism, photocontrolled tunable luminescence, and photocatalytic activity.

Highly Efficient Cuprous Complexes with Thermally Activated Delayed Fluorescence for Solution-Processed Organic Light-Emitting Devices

Two mononuclear cuprous complexes [Cu(PNNA)(POP)]BF4 (1) and [Cu(PNNA)(Xantphos)]BF4 (2) (PNNA = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-3-yl)-9,10-dihydroacridine, POP = bis[2-(dipenylphosphino)phenyl]ether, Xantphos =4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), with intense bluish-green luminescence based on a new diimine ligand were designed and synthesized. Their structural, electrochemical, and photophysical properties were characterized by single-crystal X-ray analysis, cyclic voltammetry, temperature dependence of spectroscopy, time-dependent emission spectroscopy, etc. The complexes exhibit high photoluminescence quantum yields in doped films (up to 74.6%) at room temperature. Thermally activated delayed fluorescence based on intraligand charge transfer was observed by grafting a strong electron-donor moiety, 9,9-dimethylacridan, on the diimine ligand, which is supported by the density functional theory calculations on two complexes. Highly efficient solution-processed OLEDs based on these two complexes were fabricated, among which the electroluminescent device using 2 as dopant shows a peak external quantum efficiency of 7.42%, a peak current efficiency of 20.24 cd/A, and a maximum brightness of 5579 cd/m(2).

Polyoxometalate anion–π interaction-directed assembly of a three-dimensional hydrogen-bonded supramolecular framework with nanoscale porosity

A rare three-dimensional hydrogen-bonded supramolecular framework composed of octahedral [Cr(H3O)3(H2O)3]6+ ions and linear π-electron-deficient N,N′-di(4-pyridyl)-1,4,5,8-naphthalenediimide (DPNDI) tectons was formed in the presence of electron-rich polyoxometalates by less common noncovalent anion–π interactions, indicating that polyoxometalates dominated self-assembly with anion–π interactions.

Combining Charge‐Transfer Pathways to Achieve Unique Thermally Activated Delayed Fluorescence Emitters for High‐Performance Solution‐Processed, Non‐doped Blue OLEDs

Two efficient blue thermally activated delayed fluorescence compounds, B-oCz and B-oTC, composed of ortho-donor (D)-acceptor (A) arrangement were designed and synthesized. The significant intramolecular D-A interactions induce a combined charge transfer pathway and thus achieve small ΔEST and high efficiencies. The concentration quenching can be effectively inhibited in films of these compounds. The blue non-doped organic light emitting diodes (OLEDs) based on B-oTC prepared from solution processes shows record-high external quantum efficiency (EQE) of 19.1 %.

A new POM–MOF hybrid microporous material with ultrahigh thermal stability and selective adsorption of organic dyes

Using Keggin heteropolyoxometalate H3PW12O40 as the template, a new host–guest POM–MOF hybrid material formulated as (CH3NH2CH3)[Cu2(TPB)2 (PW12O40)]·4DMF·6H2O (1) has been successfully synthesized under solvothermal conditions. Complex 1 is characteristic of a 3D host framework constructed from Cu+ ions and TPB ligands and containing different types of one-dimensional channels. The larger channels along the c axis are occupied by Keggin polyoxoanions as guests, while the narrower ones along the [110] direction are available to accommodate solvent molecules and counter dimethylamine cations. Complex 1 shows ultrahigh thermal stability and permanent porosity. In addition, dye adsorption and photocatalytic properties of 1 have been investigated. The results indicated that complex 1 is not only a good heterogeneous photocatalyst for the degradation of MO−, but also selectively captures MB+ from binary mixtures of MB+/MO−, MB+/R6G+ or MB+/RhB+.

Anion-π Interaction-Induced Room-Temperature Phosphorescence of a Polyoxometalate-Based Charge-Transfer Hybrid Material

Room-temperature phosphorescence (RTP) was realized for the first time in a polyoxometalate-based charge-transfer (CT) hybrid material bearing polyoxometalates (POMs) as electron-donors (D) and rigid naphthalene diimides (NDIs) as electron-acceptors (A), meanwhile, this hybrid material displayed photochromism as well. The significant D-A anion-π interaction induced an additional through-space charge-transfer pathway. The resulting suitable D-A CT states can efficiently bridge the relatively large energy gap between the NDI-localized 1 π-π* and 3 π-π* states and thus trigger the ligand-localized phosphorescence (3 π-π*).

Synthesis, Structural Characterization of a Novel Ferrocene Derivative and Preliminarily Anticancer Activity

A novel structure of ferrocene derivative 1 was synthesized with cyanuric chloride and ferrocenemethanol as starting materials. The synthesized compound was fully characterized using 1H NMR, 13C NMR, MS and XRD. Subsequently, the in vitro anticancer effect against A549, HCT116 and MCF-7 cell lines was preliminarily evaluated by the MTT method. The result showed that this compound exhibits good cytotoxic effect on A549, HCT116 and MCF-7 cell lines.