Three‐Component Self‐Assembly Changes its Course: A Leap from Simple Polymers to 3D Networks of Spherical Host–Guest Assemblies

Abstract

One‐pot self‐assembly reactions of the polyphosphorus complex [Cp*Fe(η5‐P5)] (A), a coinage metal salt AgSbF6, and flexible aliphatic dinitriles NC(CH2)xCN (x=1–10) yield 1D, 2D, and 3D coordination polymers. The seven‐membered backbone of the dinitrile was experimentally found as the borderline for the self‐assembly system furnishing products of different kinds. At x<7, various rather simple polymers are exclusively formed possessing either 0D or 1D Ag/A structural motifs connected by dinitrile spacers, while at x≥7, the self‐assembly switches to unprecedented extraordinary 3D networks of nano‐sized host–guest assemblies (SbF6)@[(A)9Ag11]11+ (x=7) or (A)@[(A)12Ag12]12+ (x=8–10) linked by dinitriles. The polycationic nodes represent the first superspheres based on A and silver and are host–guest able. All products are characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. The assemblies [(A)12Ag12]12+ were visualized by transmission electron microscopy.

Structural Chemistry of Giant Metal Based Supramolecules

“…The chemistry of spacer-based supramolecules and especially of MOCs is a fast developing area of modern coordination chemistry. During the last decades, a large variety of new research directions was developed (synthetic and theoretical), such as the in situ generation of spacers by the subcomponent self-assembly, postassembly modification of MOCs, , usage of metalloligands in a rational way to the heterometallic MOCs, − , construction of MOCs from presynthesized metal-based secondary building blocks serving as vertices , including organometallic LM­(η n -P n ) complexes , and POMs, high-order assembly of coordination cages into 1D-3D polymeric networks. ,− …”

Multifunctional Hyphae Carbon Powering Lithium–Sulfur Batteries

“…One of the most wondrous aspects of nature is that a great many materials are formed through self‐assembly, which is a phenomenon in which aggregation of macromolecular, colloidal, and nanoscale monomers into a highly intricate and 3D architecture occurs through spontaneous process. [ 1–3 ] Generally, self‐assembly technology can be classified into two types: physicochemical self‐assembly and biological self‐assembly. [ 4–7 ] The former is usually powered by a number of non‐covalent forces such as van der Waals, π–π and hydrophobic–hydrophilic interaction, hydrogen bonding, and electrostatic force, and show great success on synthesis of various nanomaterials (metal oxides, metals, metal sulfides, carbon and so on).…”

Chain Length Effect on the Structural and Emission Properties of the CuI/Bis((4-methoxyphenyl)thio)alkane Coordination Polymers

“…Since the pioneer works by Hardt and Holdt in the late 70s − and later by Ford and his collaborators in the 80s on neutral copper­(I) halide clusters Cu x X x L y (X = I; 2, 4, y = 4), this chemistry has been extended to a larger family of Cu x X x L y -containing complexes and coordination polymers (CP; X = Cl, Br, I, OH; 2 < x < 8, y = 4...). − This field is largely dominated by N- and P-donor ligands, and significant advances in the field of material science have been made. − In particular, when X = I, for the clusters, namely the closed-cubane Cu 4 I 4 , the resulting responsive materials turn out to be strongly emissive, and properties such as vapo-, solvato-, mechano-, and thermochromism have been reported. ,,− The effect of the aliphatic chain length variation that connects two NC/P-donor units with ditopic linkers on the outcomes of their coordination chemistry on coinage metal ions was also previously studied. − …”