Diamondoid Supramolecular Coordination Frameworks from Discrete Adamantanoid Platinum(II) Cages

Abstract

Recently, porous framework materials with various network-type structures have been constructed via several different approaches, such as coordination interactions, reversible covalent bonds, and non-covalent interactions. Here, we have combined the concepts of supramolecular coordination complex (SCC) and metal-organic framework to offer a new strategy to construct a diamondoid supramolecular coordination framework (SCF) from an adamantanoid supramolecular coordination cage as the tetrahedral node and a difunctional Pt(II) ligand as the linear linker via stepwise orientation-induced supramolecular coordination. The adamantanoid supramolecular coordination cage has four uncoordinated pyridyl groups, which serve as the four vertexes of the tetrahedral geometry in the diamondoid framework. As a result, this diamondoid SCF exhibits an adamantanoid-to-adamantanoid substructure with two sets of pores, including the interior cavity of the adamantanoid cage and the extended adamantanoid space between the individual cages in the framework. In addition, the shape-controllable and highly ordered self-assembly of nanometer-sized diamondoid SCF is observed as micrometer-sized regular octahedrons by evaporation under heating in DMSO. This study demonstrates the potential application of supramolecular coordination complexes in the precise construction of highly regulated porous framework materials.

Coordinative-to-covalent transformation, isomerization dynamics, and logic gate application of dithienylethene based photochromic cages

“…One-pot component self-assembly of versatile coordination architectures has aroused great interest in recent years. In particular, via the synergetic formation of dynamic covalent imine bonds (C]N) and coordination bonds, a variety of fascinating structures have been constructed, including cages, [1][2][3][4][5][6][7][8][9][10][11][12] helicates, [13][14][15][16] capsules, [17][18][19][20] borromeates, [21][22][23] catenanes [24][25][26][27] and rotaxanes. [28][29][30][31] Multi-component self-assembly of pure covalent-organic cage-like architectures with well-dened complexity and integrity has been achieved, [32][33][34][35] but the use of metallo-components may provide further control of the process by preorientation through metal ion coordination.…”

Syntheses and Crystal Structures of Two Cadmium Methanetetrabenzoates Featured by Open Framework and Infinite Layers

“…Common examples are the mineral melanophlogite and various porous silica modifications. A platinum coordination compound with adamantoid cages has been reported very recently . Further three‐dimensional and porous coordination polymers have been prepared using tetrahedral building units, like the anions of methanetetra‐ p ‐benzoic acid and tetrakis(4‐carboxy‐phenyl)silane .…”

Syntheses and Crystal Structures of Two Cadmium Methanetetrabenzoates Featured by Open Framework and Infinite Layers

“…A platinum coordination compound with adamantoid cages has been reported very recently. [ 11 ] Further three-dimensional and porous coordination polymers have been prepared using tetrahedral building units, like the anions of methanetetra-p-benzoic acid and tetrakis(4-carboxyphenyl)silane. [12− 15 ] A few three-dimensional open frameworks have been reported for the connection between the methanetetra-p-benzoate anion (MTB 4− ) and metal cations (Ni 2+ , Co 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Zr 4+ , Pb 2+ ).…”

“…The connection between the [MTB] Selected bond lengths and angles of the MTB 4anion and the 2,2′bipyridine molecules in Cd4(2,2′-bipy)4(µ7-MTB)2)−O(3) 128.7(9) C(29)−O(7)125.5(11) …”