Construction of a 2D Rectangular Grid and 3D Diamondoid Interpenetrated Frameworks and Their Functionalities by Changing the Second Spacers

Three new metal–organic Zn II frameworks, {[Zn(bipy)(1,4‐ndc)(H 2 O) 2 ] · 2H 2 O} ( 1 ), {[Zn(bpe)(1,4‐ndc)] 2 · 2DMF} ( 2 ), {[Zn(bpee)(1,4‐ndc)] 2 · 2DMF} ( 3 ) [bipy = 4,4′‐bipyridyl, 1,4‐ndc = 1,4‐naphthalenedicarboxylate, bpe = 1,2‐bis(4‐pyridyl)ethane, bpee = 1,2‐bis(4‐pyridyl)ethylene], have been synthesized by using mixed‐ligand systems under solvothermal conditions and characterized structurally by single‐crystal X‐ray diffraction. Compound 1 has a 2D structure with 4 4 ‐ sql net topology, whereas 2 and 3 have a 3D diamondoid structure with interesting fourfold interpenetrated topology. Topological analyses of the diamondoid nets in compounds 2 and 3 reveal a 4‐connected net with 6 6 topology. Thermogravimetric experiments suggest that the solvent‐free compounds 1 – 3 are stable up to 370, 330, and 280 °C, respectively. The grids of 1 stack in –ABCD– fashion without any regular channel structure. Desolvated compound 2 ( 2′ ) selectively adsorbs CO 2 over N 2 , and such discrimination is regulated by the restricted window dimension of the channels. Solvent vapor (H 2 O, MeOH, and EtOH) adsorption studies with 2′ suggest a hydrophobic nature of the pore surface. Gas and vapor adsorption studies with 3′ reveal no uptake, which can be correlated to a smaller pore size relative to the kinetic diameter of the respective adsorbates.