Skeleton Carbonylation of Conjugated Microporous Polymers by Osmium Catalysis for Amine-Rich Functionalization.

This work introduces a new efficient method for the postsynthetic modification of conjugated microporous polymers (CMPs). Osmium catalysis of hollow CMP (H-CMP) in the presence of NaClO3 resulted in the conversion of alkynes in the skeleton of CMPs to dicarbonyl groups to form H-CMP-DC. Through controlling the reaction time, the carbonylation degree of H-CMP could be managed, maintaining hollow morphology. We verified the benefits of carbonyl groups in H-CMP-DC in the removal of Cr(VI) from water. Imination of H-CMP-DC resulted in amine-rich H-CMP (H-CMP-A), which showed enhanced adsorption performance toward Cr(VI) in water with qmax up to 73 mg/g, compared with the H-CMP and H-CMP-DC. The H-CMP-A could be recycled at least five times, maintaining its original adsorption ability.

In Situ Water-Compatible Polymer Entrapment: A Strategy for Transferring Superhydrophobic Microporous Organic Polymers to Water.

Microporous organic polymer nanoparticles bearing tetraphenylethylene moieties (MOPTs) were prepared in the presence of poly(vinylpyrrolidone) (PVP). The PVP was entrapped into the microporous network of MOPT to form MOPT-P and played the roles of size control, porosity enhancement, and surface property management. MOPT materials without PVP showed superhydrophobicity with a water contact angle of 151°. In comparison, the MOPT-P showed excellent water compatibility. Moreover, due to the aggregation-induced emission property of tetraphenylethylene moieties, the MOPT-P showed emission and excellent emission-based sensing of nitrophenols in water with Ksv values in the range of 1.26 × 104 ∼ 3.37 × 104 M-1. It is noteworthy that the MOPT-P used water only as a sensing medium and did not require additional organic solvents to enhance water dispersibility of materials. The MOPT-P could be recovered and reused for the sensing at least five times.

Hollow and microporous triphenylamine networks post-modified with TCNE for enhanced organocathode performance.

Hollow microporous triphenylamine networks (H-MTPN) were post-modified with tetracyanoethylene (TCNE) to generate tetracyanobutadiene moieties in H-MTPN-TCNE. The H-MTPN-TCNE showed the improved electrochemical performance of cathode materials for lithium ion batteries, compared to the original H-MTPN.

Dual role of Cu2O nanocubes as templates and networking catalysts for hollow and microporous Fe-porphyrin networks.

Cu2O nanocubes were used for the synthesis of hollow and microporous Fe porphyrin networks (H-MFePN). In this synthesis, Cu2O nanocubes performed not only as networking catalysts but also as shape controlling templates. MFePN were formed on the surface of the Cu2O nanocubes through azide-alkyne cycloaddition of tetrakis(4-ethynylphenyl) Fe-porphyrin with 1,4-diazidobenzene. H-MFePN showed excellent catalytic activities in carbene insertion into N-H bonds, maintaining their activities during five recycle tests.

Hollow Microporous Organic Networks Bearing Triphenylamines and Anthraquinones: Diffusion Pathway Effect in Visible Light-Driven Oxidative Coupling of Benzylamines.

Hollow microporous organic networks were prepared by using silica spheres as the template and tris(4-ethynylphenyl)amine and 2,6-diiodo-9,10-anthraquinone as the building blocks for the Sonogashira coupling. The resultant materials bearing triphenylamine and anthraquinone moieties showed efficient visible light absorption and catalytic activities in the photochemical oxidative coupling of benzylamines. Through the comparison studies of hollow and nonhollow catalytic materials, the diffusion pathway effect of the substrates was clearly observed in the photochemical conversion of benzylamines.

Engineering of Sn-porphyrin networks on the silica surface: sensing of nitrophenols in water.

Sn-porphyrin networks were engineered on the surface of a thin layer chromatography (TLC) plate via Sonogashira coupling of the Sn-porphyrin building block and 1,4-diiodobenzene. The Sn-porphyrin film showed a strong Soret band absorption at 422 nm, emission at 600-630 nm, and excellent sensing performance toward nitrophenols in water.

Graphene-based electrochromic systems: the case of Prussian Blue nanoparticles on transparent graphene film.

Prussian Blue nanoparticles were electrodeposited on transparent grapheme film, which showed a promising electrochromism with response times in the range of 3.3-38 s.

Phenothiazine-based organic dyes with two anchoring groups on TiO2 for highly efficient visible light-induced water splitting.

New phenothiazine-based organic dyes with two anchoring groups at 3,7 positions and systematic alkyl chains on nitrogen were prepared. Their TiO(2)-Pt composites showed excellent photo-catalytic activities in visible light-induced water splitting. Interestingly, phenothiazine dyes with longer alkyl chains showed better stability in catalytic systems.

Photocatalysis by phenothiazine dyes: visible-light-driven oxidative coupling of primary amines at ambient temperature.

New phenothiazine based organic dyes were prepared for visible-light-driven organic transformations. The 3,7-disubstituted phenothiazine derivatives showed visible light absorption and reversible one-electron oxidation behavior. In the presence of 0.5 mol % of 3,7-disubstituted phenothiazines, primary benzylamines showed oxidative coupling under visible light irradiation from a blue LED. The electronic effect of substituents in phenothiazine dyes was observed in catalytic activities. The mechanistic pathway of oxidative coupling was discussed based on the detection of H(2)O(2) after the reaction.

Designed synthesis of ferrocenylanthraquinones and their bifunctional electrochromic properties.

New bifunctional electrochromic systems were developed by combination of reductive anthraquinone with oxidative ferrocene redox systems. The resultant ferrocenylanthraquinones demonstrated enhanced stability in electrochromic performance through the concomitant reductive electrochromism and oxidative counting action. The displayed colors were dependent on the position of the ferrocenyl group.

Molecular design and preparation of bis-isophthalate electrochromic systems having controllable color and bistability.

New electrochromic systems based on bis-isophthalates were designed and prepared. They showed electrochromism behavior by two-electron reduction. The displayed colors showed greatly enhanced bistability and were dependent on the length of the conjugated bridge between the two isophthalate groups. We believe that the connection of two electrochromic systems with a conjugated bridge is a good basic strategy to obtain new bistable electrochromic systems.