Three porphyrin-based bismetallacycles are prepared multi-component metal-coordination-driven self-assembly. Owing to different tetracarboxylic ligands in their structures, they show distinct coordination geometries and stacking modes, which inhibit the self-aggregation of porphyrin and offer improved singlet oxygen generation efficiency. These bismetallacycles are successfully used for the photooxidation of methyl(phenyl)sulfane, showing their potential applications toward photocatalysis.

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http://dx.doi.org/10.1039/d2dt02197hDOI Listing

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Three porphyrin-based bismetallacycles are prepared multi-component metal-coordination-driven self-assembly. Owing to different tetracarboxylic ligands in their structures, they show distinct coordination geometries and stacking modes, which inhibit the self-aggregation of porphyrin and offer improved singlet oxygen generation efficiency. These bismetallacycles are successfully used for the photooxidation of methyl(phenyl)sulfane, showing their potential applications toward photocatalysis.

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Multicomponent coordination-driven self-assembly has proved to be a convenient approach to prepare advanced supramolecular coordination complexes (SCCs), especially for those with three-dimensional structures. Herein, we report the preparation of three tetragonal prismatic cages via the self-assembly of Pt(PEt)(OTf), three different linear dipyridyl ligands and porphyrin-based sodium benzoate ligands. Due to the efficient charge separation in the coordination process of Pt(PEt)(OTf) with pyridine and carboxylic acid and the directionality of metal-coordination bonds, these cages were prepared in high isolated yields (more than 90%).

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CO(2) selective 1D double chain dipyridyl-porphyrin based porous coordination polymers.

Dalton Trans

April 2014

Department of Chemistry and Protein Research Center for Bio-Industry, Hankuk University of Foreign Studies, Yongin 449-791, Republic of Korea.

Thermal reactions of MnCl(DPyP) (DPyP = 5,15-di(4-pyridyl)-10,20-diphenylporphyrin) as a metalloligand with Co(II) and Zn(II) ions in dimethylformamide led to neutral one-dimensional (1D) double chain dipyridyl-porphyrin-based porous coordination polymers (PCPs), Co3(DPyP)3·4DMF (I) and Zn3(DPyP)3·2DMF·4H2O (II). Both PCPs were structurally characterized by X-ray crystallography. Particularly, the central Mn(III) ion in MnCl(DPyP) was transmetallated with Co(II) or Zn(II) ions and the central Co(II) or Zn(II) ions were further coordinated to pyridyl groups of neighboring M(DPyP) (M = Co or Zn) porphyrin complexes.

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Given that energy (exciton) migration in natural photosynthesis primarily occurs in highly ordered porphyrin-like pigments (chlorophylls), equally highly ordered porphyrin-based metal-organic frameworks (MOFs) might be expected to exhibit similar behavior, thereby facilitating antenna-like light-harvesting and positioning such materials for use in solar energy conversion schemes. Herein, we report the first example of directional, long-distance energy migration within a MOF. Two MOFs, namely F-MOF and DA-MOF that are composed of two Zn(II) porphyrin struts [5,15-dipyridyl-10,20-bis(pentafluorophenyl)porphinato]zinc(II) and [5,15-bis[4-(pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II), respectively, were investigated.

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We demonstrate how a bioinspired synthetic approach can help organic linkers distinguish between different types of metal centers in metal-organic frameworks (MOFs). Modification of an organic building unit with methyl groups enables the unit to selectively coordinate to one of the two metal sites present in the MOFs. We report four new porphyrin-based, pillared-paddlewheel frameworks: PPF-11-Zn/Zn, -Co/Co, -Mn/Zn, and -Fe/Zn, where the first and second metals indicate the metal center for the porphyrin core and paddlewheel cluster, respectively.

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