Pressure-Induced Amidine Formation via Side-Chain Polymerization in a Charge-Transfer Cocrystal.

Compression of small molecules can induce solid-state reactions that are difficult or impossible under conventional, solution-phase conditions. Of particular interest is the topochemical-like reaction of arenes to produce polymeric nanomaterials. However, high reaction onset pressures and poor selectivity remain significant challenges.

Synthesis and Post-Processing of Chemically Homogeneous Nanothreads from 2,5-Furandicarboxylic Acid.

Compared with conventional, solution-phase approaches, solid-state reaction methods can provide unique access to novel synthetic targets. Nanothreads-one-dimensional diamondoid polymers formed through the compression of small molecules-represent a new class of materials produced via solid-state reactions, however, the formation of chemically homogeneous products with targeted functionalization represents a persistent challenge. Through careful consideration of molecular precursor stacking geometry and functionalization, we report here the scalable synthesis of chemically homogeneous, functionalized nanothreads through the solid-state polymerization of 2,5-furandicarboxylic acid.

Investigating H Adsorption in Isostructural Metal-Organic Frameworks M-CUK-1 (M = Co and Mg) through Experimental and Theoretical Studies.

A combined experimental and theoretical study of H adsorption was carried out in Co-CUK-1 and Mg-CUK-1, two isostructural metal-organic frameworks (MOFs) that consist of M ions (M = Co and Mg) coordinated to pyridine-2,4-dicarboxylate (pdc) and OH ligands. These MOFs possess saturated metal centers in distorted octahedral environments and narrow pore sizes and display high chemical and thermal stability. Previous experimental studies revealed that Co-CUK-1 exhibits a H uptake of 183 cm g at 77 K/1.

Solid-State Pathway Control via Reaction-Directing Heteroatoms: Ordered Pyridazine Nanothreads through Selective Cycloaddition.

Nanothreads are one-dimensional nanomaterials composed of a primarily sp hydrocarbon backbone, typically formed through the compression of small molecules to high pressures. Although nanothreads have been synthesized from a range of precursors, controlling reaction pathways to produce atomically precise materials remains a difficult challenge. Here, we show how heteroatoms within precursors can serve as "thread-directing" groups by selecting for specific cycloaddition reaction pathways.

Magnetism and Luminescence of a MOF with Linear Mn Nodes Derived from an Emissive Terthiophene-Based Imidazole Linker.

A new terthiophene-based imidazole luminophore 5,5'-(1-thieno[3,4-d]imidazole-4,6-diyl)bis(thiophene-2-carboxylic acid) (TIBTCH, ) was synthesized in one step from previously reported 4,6-di(thiophen-2-yl)-1-thieno[3,4-d]imidazole (DTTI, ), and their photophysical properties were studied and compared accordingly. Under solvothermal conditions, reacting with Mn(OAc) yielded a new three-dimensional metal-organic framework (MOF, ) which was structurally defined by single-crystal X-ray diffraction. In , all Mn(II) ions octahedrally bind to carboxylate- atoms to form a linear Mn secondary building unit (SBU) that contains three distinct coordination modes.

Reversible Solid-State Isomerism of Azobenzene-Loaded Large-Pore Isoreticular Mg-CUK-1.

A large-pore version of Mg-CUK-1, a water-stable metal-organic framework (MOF) with 1-D channels, was synthesized in basic water. Mg-CUK-1L has a BET surface area of 2896 m g and shows stark selectivity for CO sorption over N, O, H, and CH. It displays reversible, multistep gated sorption of CO below 0.

In situ formation and solid-state oxidation of a triselenane NSeN-pincer MOF.

Controlled partial decomposition of 2-selenonicotinic acid in the presence of Co2+ or Ni2+ resulted in the in situ formation of an unusual MOF based on triselenane ligands (RSeSeSeR) coordinated to M2+ centers as NSeN-pincers. Post-synthetic oxidation by treatment with aqueous H2O2 facilitates its solid-state conversion into a RSeO2- molecular coordination complex, which was tracked via powder X-ray diffraction studies and by single-crystal structural resolution of the final product.

Organoarsine Metal-Organic Framework with cis-Diarsine Pockets for the Installation of Uniquely Confined Metal Complexes.

ACM-1 is the first example of an organoarsine metal-organic framework (MOF), prepared using a new pyridyl-functionalized triarylarsine ligand coordinated to Ni(II) nodes. ACM-1 has micropores that are decorated with cis-diarsine coordination pockets. Postsynthetic metalation of ACM-1 with AuCl under facile conditions studied by single-crystal X-ray diffraction reveals the installation of dimeric AuCl complexes via the formation of As-Au bonds.

A Metal-Organic Framework with Cooperative Phosphines That Permit Post-Synthetic Installation of Open Metal Sites.

PCM-101 is a phosphine coordination material comprised of tris(p-carboxylato)triphenylphosphine and secondary pillaring groups coordinated to [M (OH)] nodes (M=Co, Ni). PCM-101 has a unique topology in which R P: sites are arranged directly trans to one another, with a P⋅⋅⋅P separation distance dictated by the pillars. Post-synthetic coordination of soft metals to the P: sites proceeds at room temperature to provide X-ray quality crystals that permit full structural resolution.

A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State.

A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air- and moisture-stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal-organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with Pd(II) Cl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with Co(II) ions and structural resolution by single crystal X-ray diffraction.