Porous Metal−Organic Frameworks Based on Metal−Organic Polyhedra with Nanosized Cavities as Supramolecular Building Blocks:  Two-Fold Interpenetrating Primitive Cubic Networks of [Cu₆L₈]¹²⁺ Nanocages

Abstract

Discrete metal-organic polyhedra (MOP) with nanosized cavities and/or clusters of MOP could be prepared when C3-symmetric facial ligands and a potential hexatopic Cu(II) ion are combined in the presence of perchlorate as a weak linker, while similar reaction conditions in the presence of a nitrate linker led to extended metal-organic frameworks made of MOP as supramolecular building blocks.

Structures of N,N′,N′′-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide and its nano-scopic zinc(II) coordination ring and their interaction with calf thymus DNA

“…Two 3-TPB ligands and two Zn(II) ions link alternatively to form a 28-membered ring. The ZnÁ Á ÁZn distance in the ring is 11.162(5) Å, which is shorter compared with the CuÁ Á ÁCu distances in a nano-cage of 13.940(3) Å [17]. This distance is much longer than a flexible oligoamide Zn complex of 3.572 Å [26].…”

“…Lah and coworkers reported [Pd 6 (3-TPB) 8 ] 12+ cages two years later [16]. [Cu 6 (3-TPB) 8 ] 12+ nano-cages can be formed in DMSO [17]. Mononuclear Cu(I), Ag(I) complexes of the N-methyl substituted 3-TPB have also been reported.…”

Self-assembled metal–organic polyhedra: An overview of various applications

“…Lah and co-workers synthesized octahedra by reaction of Cu(II) perchlorate and N,N',N"-tris(3-pyridinylmethyl)-1,3,5-benzenetricarboxamide in dimethyl sulfoxide (DMSO). However, self-assembly of copper nitrate with C 3 symmetric ligands N,N',N"-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide and N,N',N"-tris(3-pyridinylmethyl)-1,3,5-benzenetricarboxamide forms an isoreticular metal-organic framework based on polyhedra as SBB [207]. This marginal change of counter anion from perchlorate to nitrate i.e.…”

[Cu4OCl6(DABCO)2]·0.5DABCO·4CH3OH (“MFU-5”): Modular synthesis of a zeolite-like metal-organic framework constructed from tetrahedral {Cu4OCl6} secondary building units and linear organic linkers

“…A large number of MOFs based on particular SBUs (such as the tetranuclear {Zn 4 O(CO 2 ) 6 } unit acting as octahedral node in the MOF-n series [11][12][13], the trinuclear {Ga 3 (PO 4 ) 3 F 2 } unit of the MIL-n family [14,15], or the binuclear paddle-wheel {Cu 2 (CO 2 ) 4 } unit acting as square node in many MOF structures [16][17][18][19][20][21][22][23][24]) have thus been synthesized through suitable combinations of metal salts and organic linkers [25,26], occasionally employing additional templates [2,3,[27][28][29]. However, apart from a few notable exceptions [9,[30][31][32][33], MOF topologies reported in literature have not resulted from assemblies of rationally designed SBUs. Few studies were focused on studying the particular role of SBUs during MOF formation [34][35][36][37][38].…”