Microporous organic networks (MONs) are a new class of porous materials. This work shows the application of MON chemistry for the preparation of magnetically separable catalytic systems. By the Sonogashira coupling of Fe III − tetrakis(4-ethynylphenyl)porphyrin and 1,4-diiodobenzene, Fe 3 O 4 nanoparticles were coated successfully with Fe−porphyrin networks. The average thickness of the homogeneous coating was ∼17 nm. According to the powder X-ray diffraction and N 2 isotherm analyses, the Fe−porphyrin network coating exhibited amorphous and microporous characteristics. The microporous Fe−porphyrin networks on the Fe 3 O 4 nanoparticles showed good catalytic performance for carbene insertion into the N−H bond of amines. The catalytic systems were easily recycled from the reaction mixture by magnetic separation. We believe that the synthetic strategy in this work can be extended to the various catalytic systems.

Novel iridium(III) complexes containing bis(N-heterocyclic carbene), bis(imidazoline thione) L2, and bis(imidazoline selone) L3 were prepared. The iridium complexes bearing L2 and L3 showed the significant absorption of visible light with maximum intensity at ∼460 nm. Bis(2-(2′-benzothienyl)pyridinato)iridium(III) complexes (Ir-6) with L3 showed excellent ability as a photosensitizer of visible light. Under blue LED irradiation with maximum emission at 460 nm, 0.25 mol % Ir-6 showed 94% conversion of benzylamine for 5 h at room temperature. Through mechanistic studies, it was suggested that the photoinduced oxidative coupling of benzylamine by Ir-6 follows a singlet oxygen pathway. The excellent performance of Ir-6 originated from the efficient visible light absorption at 460 nm and the enhanced triplet state due to the heavy-atom effect of L3. This work shows that bis(imidazoline thione) and bis(imidazoline selone) can be efficient ligands for tuning the optical properties of iridium(III) complexes.

S Supporting Information R ecently, various microporous organic networks (MONs) have been prepared by coupling reactions of organic building blocks. 1−4 For example, the Cooper research group and others have shown that the Sonogashira coupling of rigid organic building blocks results in the formation of various MON materials. 1−3,5 These materials have shown unique physical properties such as high surface area and microporosity (pore size <2 nm). 1−5 On the basis of these properties, the MON materials have been applied as gas adsorbents 1−7 and sensing materials 1,8,9 for small guests. By using tailored building blocks, various sensing moieties can be introduced into MON materials. For example, metallo-porphyrins with vacant axial coordination sites have been incorporated into MON materials to interact with guest molecules. 10−14 In these applications, the small molecules diffuse into MON materials to interact with inner active moieties. To reduce the diffusion pathway of guest molecules, our research group has studied the hollow structure engineering of MON materials based on nontemplate 15 or template methods. 16 Quartz crystal microbalance is a very useful device for gas sensing. 17 Various inorganic and organic polymeric materials have been used as sensing materials in QCM devices. 17 The porous sensing materials can enhance efficiency because the inner active species can be utilized in the sensing. 18 Although MON materials have promising potential as sensing materials, as far as we are aware, their application to QCM devices has not been reported. MON materials prepared without templates usually have irregular shape and size. In our preliminary studies on the application of nonhollow and irregular MON granules bearing metallo-porphyrins to QCM devices, the materials showed very poor performance as sensing materials. In this work, we report the synthesis of hollow and microporous Zn−porphyrin networks (HMZnP) with controlled outer shapes and their shape dependent ammonia sensing performance in QCM devices. Figure 1 shows a synthetic route for the shape controlled HMZnP materials. For preparation of polyhedral HMZnP (P-HMZnP), polyhedral ZIF-8 nanocrystals were prepared by procedures in the literature. 19,20 Microporous (metal-free) porphyrin network (MP) was formed on the surface of ZIF-8 via the Sonogashira coupling of tetrakis(4-ethynylphenyl)porphyrin with 1,4-diiodobenzene (See Experimental Sections in the Supporting Information, SI). The inner ZIF-8 in ZIF-8@MP was completely etched by treatment of hydrochloric acid to form hollow and microporous porphyrin networks with a polyhedral shape (P-HMP). The reaction of P-HMP with zinc acetate resulted in the P-HMZnP. When Zn−porphyrin building blocks with four terminal alkynes were used instead of metal-free porphyrins, the Zn in porphyrin was decoordinated during the acidic etching process. Thus, the Zn was introduced to P-HMP by post-synthetic modification. Spherical HMZnP (S-HMZnP) was prepared using silica nanospheres as templates, instead of ZIF-8 nanocr...

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.

Synurus deltoides Aiton, Nakai, is an edible plant that has been used as a folk medicine for treating inflammatory disorders. This investigation was carried out to establish the antiinflammatory activity of this plant material using a 75% ethanol extract from the aerial part of S. deltoides. Against the acute inflammatory animal model of mouse croton oil-induced ear oedema assay, the extract did not show significant inhibition at 100-800 mg/kg by oral administration. On the other hand, the extract showed considerable inhibition against the chronic inflammatory animal model of rat adjuvant-induced arthritis (25% inhibition at 100 mg/kg/day) while prednisolone exerted 40% inhibition at 10 mg/kg/day. In addition, S. deltoides possessed strong analgesic activity (IC50 = 50 mg/kg) in the acetic acid-induced writhing test. From the extract, ursolic acid and scopoletin were successfully isolated and their contents were found to be 0.31% and 0.37% (w/w), respectively, based on the dried extract by HPLC analysis. All the results obtained indicate that this plant material may be used beneficially as an antiinflammatory agent having analgesic action.

This work reports on the controllable guest entrapment and release behavior of microporous organic hollow spheres (MOHs). Porphyrins which are soluble in both water and methanol were entrapped in the MOHs using methanol solution. The water-soluble porphyrins entrapped in MOHs were not extracted by water due to the hydrophobicity of microporous organic shells. In contrast, the porphyrins were released gradually into aqueous solution by adding water-soluble organic solvents. The release behavior depended on the kind of organic solvents used and on the alkyl chain length of the porphyrin compounds. These properties were applied for the fluorescent alert towards the existence of organic solvents in flowing aqueous media.

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