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.
Eintopf‐Selbstorganisationsreaktionen des Polyphosphor‐Komplexes [Cp*Fe(η5‐P5)] (A), des Münzmetallsalzes AgSbF6 und flexibler aliphatischer Dinitrile NC(CH2)xCN (x=1–10) geben 1D‐, 2D‐ und 3D‐Koordinationspolymere. Die siebengliedrige Kette eines Dinitrils wurde experimentell als Grenze für das Selbstorganisationssystem zur Erzeugung verschiedenartiger Produkte detektiert. Bei x<7 werden ausschließlich verschiedene, eher einfache Polymere gebildet, die entweder 0D‐ oder 1D‐Ag/A‐Strukturmotive besitzen, die durch Dinitril‐Linker verbunden sind, während bei x≥7 die Selbstorganisation zu völlig neuen außergewöhnlichen, durch Nitrile verbundenen 3D‐Netzwerken nano‐dimensionierter Wirt/Gast‐Aggregate von (SbF6)@[(A)9Ag11]11+ (x=7) oder (A)@[(A)12Ag12]12+ (x=8–10) wechselt. Die polykationischen Knoten stellen die ersten auf A und Silber basierenden Supersphären dar, die Wirt/Gast‐fähig sind. Alle Produkte wurden durch NMR‐Spektroskopie, Massenspektrometrie und Einkristall‐Röntgenstrukturanalyse charakterisiert. Die Aggregate [(A)12Ag12]12+ wurden durch Transmissionselektronenmikroskopie visualisiert.
Pentaphosphaferrocenes [Cp R Fe(η 5 -P 5 )] (Cp* = η 5 -C 5 Me 5 ) (A), Cp'' = η 5 -C 5 H 3 tBu 2 -1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF 6 . Adding rigid aromatic dinitriles ortho/meta/para-(NC) 2 C 6 H 4 in a one-pot reaction between [Cp R Fe(η 5 -P 5 )] and AgSbF 6 leads to various coordination polymers (CPs) by a three-component self-assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC) 2 C 6 H 4 play a key role in the formation of the isolated CPs. All CPs were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal Xray diffraction.
Background/Aim: Our studies have shown that an avocado extract (D003) selectively inhibits proliferation in premalignant and malignant but not normal primary human oral epithelial cell lines via an ROS-mediated mechanism. Herein, the in vivo anticancer effect of D003 extract and freeze-dried avocado (FA) was determined in the DMBAinitiated hamster cheek pouch (HCP) model.
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