Applying the Power of Reticular Chemistry to Finding the Missing alb-MOF Platform Based on the (6,12)-Coordinated Edge -Transitive Net

Highly connected and edge-transitive nets are of prime importance in crystal chemistry and are regarded as ideal blueprints for the rational design and construction of metal organic frameworks (MOFs). We report the design and synthesis of highly connected MOFs based on reticulation of the sole two edge-transitive nets with a vertex figure as double six-membered ring (d6R) building unit, namely the (4,12)-coordinated shp net (square and hexagonal-prism) and the (6,12)-coordinated alb net (aluminum diboride, hexagonal-prism and trigonal-prism). Decidedly, the combination of our recently isolated 12-connected (12-c) rare-earth (RE) nonanuclear [RE9(mu(3)-OH)(12)(mu(3)-O)(2)(O2C-)(12)] carboxylate-based cluster, points of extension matching the 12 vertices of hexagonal-prism d6R, with 4-connected (4c) square porphyrinic tetracarboxylate ligand led to the formation of the targeted RE-shp-MOF. This is the first time that RE-MOFs based on 12-c molecular building blocks (MBBs), d6R building units, have been deliberately targeted and successfully isolated, paving the way for the long-awaited (6,12)-c MOF with alb topology. Indeed, combination of a custom-designed hexacarboxylate ligand with RE salts led to the formation of the first related alb-MOF, RE-alb-MOF. Intuitively, we successfully transplanted the alb topology to another chemical system and constructed the first indium-based alb-MOF, In-alb-MOF, by employing trinuclear [In-3(mu(3)-O)(O2C-)(6)] as the requisite 6 connected trigonal-prism and purposely made a dodecacarboxylate ligand as a compatible 12-c MBB. Prominently, the dodecacarboxylate ligand was employed to transplant shp topology into copper-based MOFs by employing the copper paddlewheel [Cu-2(O2C-)(4)] as the complementary square building unit, affording the first Cu-shp-MOF. We revealed that highly connected edge-transitive nets such shp and alb are ideal for topological transplantation and deliberate construction of related MOFs based on minimal edge-transitive nets.