De Novo Tailoring Pore Morphologies and Sizes for Different Substrates in a Urea-Containing MOFs Catalytic Platform

To better understand the structure–catalytic property relationship, a platform of urea-containing MOFs with diverse topologies as hydrogen-bonding (H-bond) catalyst has been well established in the present work. During the construction of MOFs, we proposed a new strategy called the isoreticular functionalization approach in which the desired topological net is first considered as a blueprint, and then two predesigned functionalized polydentate ligands link to four different metal clusters by de novo routes to achieve the MOFs with expected pore structure and catalytic sites. By means of this strategy, we successfully synthesized four programmed MOFs (named as <b>URMOF-1–4</b>) with diverse topologies, pore morphologies, and sizes and distribution of active sites. Subsequently, we systematically investigated the Friedel–Crafts reactions of 1-methylpyrrole or 1-methylindole with nitroalkene derivatives with diverse sizes to assess the catalytic properties of the above-mentioned URMOFs. These four URMOFs can act as reusable H-bond catalysts and show varied catalytic capacities and size-selectivity properties. Most significantly, the open morphologies of pores, large channels in the framework, and effective distribution of active sites on the wall of the channel are proved to facilitate catalysis. This urea-containing MOF catalytic platform provides new insight into the catalytic properties of MOFs with the same kind of active sites but diverse topologies, pore morphologies, and sizes and distributions of catalytic sites

In Situ Construction of a Coordination Zirconocene Tetrahedron

The current study describes the first in situ synthesis and characterization of a new family of cationic coordination tetrahedra of both the V₄F₄ and V₄E₆ type, which are constructed by a new building block based on a trinuclear zirconocene moiety and the dicarboxylate or tricarboxylate anions

A Water and Thermally Stable Metal–Organic Framework Featuring Selective CO₂ Adsorption

A 2-fold interpenetrated microporous MOF [Ni₂(C₂O₄)­(L)₂]_<i>n</i>·6<i>n</i>H₂O (HL = 4,2′:4″,2′-terpyridine-4′-carboxylic acid) (<b>1</b>) was synthesized and structurally characterized. <b>1</b> has obvious 1D channels along the crystallographic <i>a</i> and <i>c</i> axes with a pore size of 5.7 to 6.9 Å. Topological analysis shows that the framework of <b>1</b> can be interpreted as a (3,4)-connected net with point symbol (6³)­(6⁵·8). <b>1</b> exhibits high water and thermal stability, which is demonstrated by TGA, PXRD, and VT-PXRD. Additionally, the high temperature structure of <b>1</b>′ (433 K) undoubtedly demonstrates the stability of the framework. More importantly, <b>1</b> shows high selectivities for CO₂ over N₂, H₂, and CH₄ at low pressure and 273 K

In Situ Construction of a Coordination Zirconocene Tetrahedron

The current study describes the first in situ synthesis and characterization of a new family of cationic coordination tetrahedra of both the V₄F₄ and V₄E₆ type, which are constructed by a new building block based on a trinuclear zirconocene moiety and the dicarboxylate or tricarboxylate anions

In Situ Construction of a Coordination Zirconocene Tetrahedron

The current study describes the first in situ synthesis and characterization of a new family of cationic coordination tetrahedra of both the V₄F₄ and V₄E₆ type, which are constructed by a new building block based on a trinuclear zirconocene moiety and the dicarboxylate or tricarboxylate anions