Permanent Porosity Derived From the Self‐Assembly of Highly Luminescent Molecular Zinc Carbonate Nanoclusters

Rational Design of Noncovalent Diamondoid Microporous Materials for Low-Energy Separation of C6-Hydrocarbons

“…The calculation of Brunauer−Emmett−Teller surface area (S BET ) for DiaMM-1 and DiaMM-2 resulted in S BET values of 831 and 904 m 2 /cm 3 , respectively, which are in excellent agreement with accessible surface area (ASA) values of 846 and 921 m 2 /cm 3 , calculated with Poreblazer. 21 Static and Dynamic Sorption Studies of C 6 -Hydrocarbons in DiaMM-n. Having proved the structural robustness and pore accessibility of the DiaMM-n systems, we proceeded to evaluate the accessibility of their micropores to C 6 -hydrocarbons (hexane isomers, cyclohexane and benzene) by means of static single-component equilibrium isotherms at 293 K, dynamic variable-temperature pulse gas chromatography, breakthrough curves, solid state 13 C and 19 F crosspolarization magic angle spinning NMR spectroscopy (CP-MAS NMR), and computational modeling (Figure 4). For hexane isomers, the adsorption isotherms demonstrate the accessibility of the microporous network to all molecules.…”

“…This trend can be observed for both materials; however for the more omniphobic DiaMM-2 all isotherms are shifted to higher p/p 0 values, indicative of considerably weaker adsorbate−adsorbent interactions. Solid state 13 C CP-MAS NMR spectra of DiaMM-1 (Figures S10, S11) show that the line width of the carbon signals corresponding to the benzene residues decreases while the signals corresponding to the methyl groups shift downfield on going from n-hexane to bulkier 2,3-dimethylbutane. These results are indicative of stiffening of the structure upon loading with the most strongly binding alkanes.…”

“…However, the rational construction of porous structures based on van der Waals forces is challenging since discrete molecules tend to form close-packed solids with minimal void volume. 13,14 We have previously demonstrated that discrete zinc carboxylate and carbonate clusters can form diverse types of NPM structures ranging from zeolitic topologies to porous materials with voids or open channels, 15 with the diamondoid WUT-1 material being able to adsorb small probe gases. 13 Thus, our working hypothesis was (1) the diamondoid cubic lattice possesses the lowest packing density among prototypical networks (crystal packing factor of 34%, Figure 1d…”

tert‐Butyl(tert‐butoxy)zinc Hydroxides: Hybrid Models for Single‐Source Precursors of ZnO Nanocrystals

“…Based on our experience in the synthesis of alkylzinc alkoxides,8 hydroxides,6a–c,e, 8b and oxides,6d, 9 herein we describe the efficient synthesis of unique mixed tert ‐butyl( tert ‐butoxy)zinc hydroxide aggregates, [( t Bu) 4 Zn 4 (μ 3 ‐O t Bu) x (μ 3 ‐OH) 4− x ]. These compounds were obtained from a combination of the well‐defined molecular alkylzinc hydroxide [ t BuZn(μ 3 ‐OH)] 6 ( 1 6 )6e and the corresponding zinc alkoxide [ t BuZn(μ 3 ‐O t Bu)] 4 ( 2 4 ) 8a.…”

A novel organometallic macrocycle based on half-sandwich ruthenium motif

“…A difunctional pyridyl-substituted 8-hydroxyquinoline ligand is promisingly meeting the requirements. The groups of Lewiński and Yuan have reported that using 8-hydroxyquinoline-based organic ligands as linkers to assemble plethoric metal-orgnaic frameworks exhibiting unusual optical properties [19][20][21][22]. This inspired us to use the analogues to rational design and controllable synthesize metallacycles based on half-sandwich iridium, rhodium and ruthenium fragments.…”