Single-Walled Polytetrazolate Metal–Organic Channels with High Density of Open Nitrogen-Donor Sites and Gas Uptake

The self-assembly between zinc dimer and 1,3,5-tris­(2<i>H</i>-tetrazol-5-yl)­benzene (H₃BTT), promoted by a urea derivative, leads to a highly porous 3D framework with a large percentage (67%) of N-donor sites unused for bonding with metals. The material exhibits high gas storage capacity (ca. 1.89 wt % H₂ at 77 K and 1 atm; 98 cm³/g CO₂ at 273 K and 1 atm), even in the absence of open metal sites. The high percentage of open N-donor sites, coupled with the low framework density resulting from single-walled channels, is believed to contribute to the high uptake capacity

Single-Walled Polytetrazolate Metal–Organic Channels with High Density of Open Nitrogen-Donor Sites and Gas Uptake

The self-assembly between zinc dimer and 1,3,5-tris­(2<i>H</i>-tetrazol-5-yl)­benzene (H₃BTT), promoted by a urea derivative, leads to a highly porous 3D framework with a large percentage (67%) of N-donor sites unused for bonding with metals. The material exhibits high gas storage capacity (ca. 1.89 wt % H₂ at 77 K and 1 atm; 98 cm³/g CO₂ at 273 K and 1 atm), even in the absence of open metal sites. The high percentage of open N-donor sites, coupled with the low framework density resulting from single-walled channels, is believed to contribute to the high uptake capacity

Entrapment of Metal Clusters in Metal–Organic Framework Channels by Extended Hooks Anchored at Open Metal Sites

Reported here are the new concept of utilizing open metal sites (OMSs) for architectural pore design and its practical implementation. Specifically, it is shown here that OMSs can be used to run extended hooks (isonicotinates in this work) from the framework walls to the channel centers to effect the capture of single metal ions or clusters, with the concurrent partitioning of the large channel spaces into multiple domains, alteration of the host–guest charge relationship and associated guest-exchange properties, and transfer of OMSs from the walls to the channel centers. The concept of the extended hook, demonstrated here in the multicomponent dual-metal and dual-ligand system, should be generally applicable to a range of framework types

Cluster Organic Frameworks Constructed from Heterometallic Supertetrahedral Cluster Secondary Building Units

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd₄Cu₆(L)₄(Ac)₇(H₂O)₄]­(Ac)·7H₂O (<b>1</b>) and [Mn₄Cu₆(L)₄(Ac)_4.5(H₂O)₉]­CuCN­(Ac)_3.5·H₂O (<b>2</b>), where H₃L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH₃COO^–, have been prepared under solvothermal conditions. <b>1</b> and <b>2</b> are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, <b>1</b> and <b>2</b> show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material

Development of Composite Inorganic Building Blocks for MOFs

A general direction for diversifying metal–organic frameworks (MOFs) is demonstrated by the synthesis of composite inorganic clusters between indium and s-, d-, and f-block elements. These previously unknown heterometallic clusters, with various nuclearity, geometry, charge, and metal-to-metal ratios, significantly expand the pool of inorganic building blocks that are highly effective for the construction of porous MOFs with high gas uptake capacity

Development of Composite Inorganic Building Blocks for MOFs

A general direction for diversifying metal–organic frameworks (MOFs) is demonstrated by the synthesis of composite inorganic clusters between indium and s-, d-, and f-block elements. These previously unknown heterometallic clusters, with various nuclearity, geometry, charge, and metal-to-metal ratios, significantly expand the pool of inorganic building blocks that are highly effective for the construction of porous MOFs with high gas uptake capacity

Entrapment of Metal Clusters in Metal–Organic Framework Channels by Extended Hooks Anchored at Open Metal Sites

Reported here are the new concept of utilizing open metal sites (OMSs) for architectural pore design and its practical implementation. Specifically, it is shown here that OMSs can be used to run extended hooks (isonicotinates in this work) from the framework walls to the channel centers to effect the capture of single metal ions or clusters, with the concurrent partitioning of the large channel spaces into multiple domains, alteration of the host–guest charge relationship and associated guest-exchange properties, and transfer of OMSs from the walls to the channel centers. The concept of the extended hook, demonstrated here in the multicomponent dual-metal and dual-ligand system, should be generally applicable to a range of framework types

Mimicking Zeolite to Its Core: Porous Sodalite Cages as Hangers for Pendant Trimeric M₃(OH) Clusters (M = Mg, Mn, Co, Ni, Cd)

A new class of zeolite-type porous materials in which 3D frameworks are covalently functionalized with crystallographically ordered pendant metal clusters have been synthesized. This work demonstrates a new paradigm for and the feasibility of functionalizing zeolite-type frameworks through the conversion of extraframework sites in mineral zeolites into part of the framework for occupation by dangling metal clusters in metal–organic frameworks

Cluster Organic Frameworks Constructed from Heterometallic Supertetrahedral Cluster Secondary Building Units

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd₄Cu₆(L)₄(Ac)₇(H₂O)₄]­(Ac)·7H₂O (<b>1</b>) and [Mn₄Cu₆(L)₄(Ac)_4.5(H₂O)₉]­CuCN­(Ac)_3.5·H₂O (<b>2</b>), where H₃L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH₃COO^–, have been prepared under solvothermal conditions. <b>1</b> and <b>2</b> are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, <b>1</b> and <b>2</b> show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material

Generalized Synthesis of Zeolite-Type Metal–Organic Frameworks Encapsulating Immobilized Transition-Metal Clusters

Zeolites are generally made from tetrahedral nodes and ditopic linkers. Reported here is a versatile method based on trifunctional ligands. With this method, two functional groups are used to form zeolitic nets, while the third one serves to immobilize metal clusters within the channels. The process is driven by the coexistence of multiple inorganic building blocks generated in the heterometallic system. The generality of this method is shown by three distinct metal–organic frameworks mimicking AlPO₄-5 (<b>AFI</b>) and <b>BCT</b> zeotypes as well as the cubic <b>lcs</b> topology. The correlation between the framework topology and trapped metal species reveals the unique bidirectional control (framework topology ↔ confined metal species) that may be exploited to create a large family of zeotypes with channels modified by different metal ions and clusters