Metal-organic frameworks (MOFs) with negatively charged frameworks are suitable for selectively encapsulating cationic guest ions via ac ation-exchange process. Encapsulating photoactive [RuL 3 ] 2 + polypyridine complexes into the preorganized mesoscale channels of a MOF is ag ood methodf or stabilizing the excited states of the complexes. Three new RuL 3 @InBTB MOFs were prepared by encapsulating cationic [Ru(bpy) 3 ] 2 + (bpy = 2,2'bipyridine), [Ru(phen) 3 ] 2 + (phen = 1,10-phenanthroline), and [Ru(bpz) 3 ] 2 + (bpz = 2,2'-bipyrazine) into the mesopores of at hree-dimensional (3D) InBTB MOF (H 3 BTB = 1,3,5-benzenetribenzoic acid). The photophysical properties of the resultingm aterials were investigated by photoluminescence (PL) analysis. The photoredox catalytic activities were also investigated for the aza-Henry reaction,h ydrogenation of dimethyl maleate, and decomposition of methylo rangeu nder visible light irradiation at room temperature. RuL 3 @InBTB MOFs were found to be very stable and highly recyclable photoredox catalytic systems.

The encapsulation of various types of guest molecules into the preorganized channels of metal-organic frameworks (MOFs) is continuously motivating chemists searching for better MOF host materials to systematically alter or control the photophysical properties of the captured guests in a controlled manner. The unique spatial distribution and a certain preferential geometry of the guests inside MOFs often render guests to exhibit distinct optical properties. Three different viologen cations were encapsulated into the mesoscale channels of negatively charged InBTB MOF ([Et 2 NH 2 ] 3 [In 3 (BTB) 4 ]Á10DEFÁ14H 2 O, H 3 BTB = 1,3,5-benzenetribenzoic acid) via cation exchange process. The cationic viologens were partially encapsulated through cation exchange with [Et 2 NH 2 ] + counter-cations to afford viologen@InBTB. The colorless InBTB crystals changed into yellow in the case of viologen@InBTB. The fluorescence measurement of methylviologen (MV 2+) encapsulated MV@InBTB showed different behavior compared to ethylviologen (EV 2+) and benzylviologen (BV 2+) encapsulated InBTB. Both EV@InBTB and BV@InBTB exhibited unusual quenching of the photoluminescence emission in solid state.

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The heterogenized trans-[Co(en)2Cl2]+-encapsulated InBTB MOF (trans-[Co(en)2Cl2]@InBTB) catalytic system with high recyclability for oxygen evolution from hydrogen peroxide was prepared and its catalytic activity was demonstrated.

The porphyrin-based Zn-MOF is directly carbonized and activated by KOH for the generation of N-doped porous carbons acting as high performance supercapacitor electrode materials.