Directed 1D Assembly of a Ring‐Shaped Inorganic Nanocluster Templated by an Organic Rigid‐Rod Molecule: An Inorganic/Organic Polypseudorotaxane

Alam, Md. Akhtarul; Kim, Yeong‐Sang; Ogawa, Saho; Tsuda, Akihiko; Ishii, Noriyuki; Aida, Takuzo

doi:10.1002/ange.200705308

Cited by 16 publications

(6 citation statements)

References 29 publications

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“…In addition to using coordination bonds to link together organic ligands to form interlocked molecules, hybrid organic-inorganic rotaxanes have been assembled from organic threads and heterometallic rings consisting of eight or more metal ions bridged by alkylcarboxylate and fluoride anions (Scheme 61). [229,230] In a 33 component assembly process, macrocycle 165-Cr III 7 Co II forms around axle 166 to generate [2]rotaxane 167-Cr III 7 Co II . [229] Rotaxane 167-Cr III 7 Co II is a neutral molecule; the positive charge on the secondary ammonium thread is balanced by the single charge remaining on the heterometallic macrocycle consisting of 24 anionic ligands (8 fluorides and 16 pivalate groups) bound to seven trivalent Cr III cations and a single divalent Co II cation.…”

Section: Hybrid Organic-inorganic Rotaxanesmentioning

confidence: 99%

Strategies and Tactics for the Metal‐Directed Synthesis of Rotaxanes, Knots, Catenanes, and Higher Order Links

et al. 2011

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More than a quarter of a century after the first metal template synthesis of a [2]catenane in Strasbourg, there now exists a plethora of strategies available for the construction of mechanically bonded and entwined molecular level structures. Catenanes, rotaxanes, knots and Borromean rings have all been successfully accessed by methods in which metal ions play a pivotal role. Originally metal ions were used solely for their coordination chemistry; acting either to gather and position the building blocks such that subsequent reactions generated the interlocked products or by being an integral part of the rings or "stoppers" of the interlocked assembly. Recently the role of the metal has evolved to encompass catalysis: the metal ions not only organize the building blocks in an entwined or threaded arrangement but also actively promote the reaction that covalently captures the interlocked structure. This Review outlines the diverse strategies that currently exist for forming mechanically bonded molecular structures with metal ions and details the tactics that the chemist can utilize for creating cross-over points, maximizing the yield of interlocked over non-interlocked products, and the reactions-of-choice for the covalent capture of threaded and entwined intermediates.

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Section: Hybrid Organic-inorganic Rotaxanesmentioning

confidence: 99%

Strategies and Tactics for the Metal‐Directed Synthesis of Rotaxanes, Knots, Catenanes, and Higher Order Links

et al. 2011

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“…These ring clusters date back to 1995, when the synthesis and structural analysis of gigantic mixed‐valent ring‐shaped POM cluster (NH 4 ) 28 [Mo 154 (NO) 14 O 448 H 14 (H 2 O) 70 ] ({Mo 154 } ring) was first reported by Müller et al.,5a and later this was followed by a much more facile synthesis of the analogous compound Na 14 [Mo 154 O 462 H 14 (H 2 O) 70 ]⋅400 H 2 O ( 1 , Scheme ;5b–d for further information on ring properties, see Ref. 5f–j) The diameter of the POM ring and inner void space are about 3.9 and 1.7 nm, respectively, while the height of ring is about 1.8 nm 7. Despite the great potential of ring‐shaped POMs to form porous materials, POM clusters have been greatly under‐utilized and ‐investigated, probably due to poor stability 8…”

Section: Methodsmentioning

confidence: 99%

Adsorption and Catalytic Properties of the Inner Nanospace of a Gigantic Ring‐Shaped Polyoxometalate Cluster

et al. 2009

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Porous materials with structurally well-defined nanoscale cavities (e.g., carbon nanostructures, zeolites, mesoporous silica, and coordination compounds) [1][2][3] are of great interest because of their unique properties such as adsorption, separation, exchange, and catalysis, which are all associated with the presence of a functional nanospace. In this respect, polyoxometalate clusters, which are nanosized metal-oxide macroanions built from molecular precursors with a range of unique redox and acidic properties, are ideally suited for the development of functional nanospaces but have not yet been thus explored. [4][5][6] Indeed, ring-shaped POMs have a great deal of potential for allowing creation of an exceptionally well defined and accessible nanosurfaces and nanospaces. These ring clusters date back to 1995, when the synthesis and structural analysis of gigantic mixed-valent ring-shaped POM cluster (NH 4 ) 28 [Mo 154 (NO) 14 O 448 H 14 (H 2 O) 70 ] ({Mo 154 } ring) was first reported by Müller et al., [5a] and later this was followed by a much more facile synthesis of the analogous compound Na 14 [Mo 154 O 462 H 14 (H 2 O) 70 ]·400 H 2 O (1, Scheme 1; [5b-d] for further information on ring properties, see Ref.[5f-j]) The diameter of the POM ring and inner void space are about 3.9 and 1.7 nm, respectively, while the height of ring is about 1.8 nm. [7] Despite the great potential of ringshaped POMs to form porous materials, POM clusters have been greatly under-utilized and -investigated, probably due to poor stability. [8] Because of this fundamental limitation, we opted to examine the stability and functionality of a {Mo 154 } ring encapsulated by dimethyldioctadecylammonium (DODA) cations (Scheme 1), because the DODA cation, with a length of about 2.5 nm, introduces amphiphilic-like properties into the POM-cation hybrid, and POM-DODA hybrids have shown some interesting properties, for example, for formation of Langmuir-Blodgett films. [9,10] Further, we hypothesized that encapsulation by DODA will also help to increase the stability of the nanoscale wheel cluster. Not only will nanoscale molecular assembly of the hybrid material be controlled by electrostatic interactions between the {Mo 154 }-ring polyanion and DODA cations, hydrophobic interactions between the alkyl chains should contribute to stabilization of the hybrid material in the solid state. As reported previously, [9] the POM-DODA hybrid shows high stability in CHCl 3 solution, while the ring structure of 1 is not robust in aqueous solution and the solid state (see Figures S1-S4, Supporting Information).Here we report on the inner nanospace functionality of POM-DODA hybrid (DODA) 23 [Mo 154 O 462 H 5 ]·n H 2 O (2). [11] Initially, dynamic light scattering (DLS) experiments were conducted to confirm the presence of the {Mo 154 } ring of 2 in solution and showed that the particle diameter in a solution in THF is about (4.0 AE 0.6) nm, similar to the size of the {Mo 154 } ring ( Figure S5, Supporting Information). Hence, these data are consistent wit...

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“…[90] Hybrid-Rotaxane aus organischen Strängen und heterometallischen Ringen aufgebaut, die aus acht oder mehr durch Alkylcarboxylate und Fluoridanionen verbrückten Metallionen bestehen (Schema 61). [229,230] [2]rotaxanen an Co III hergestellt worden war (Schema 62). [232] Ein auf Cyclodextrin basierendes [5]Rotaxan wurde von Osakada und Mitarbeitern beschrieben, welches auf einer Pd II -bzw.…”

Section: Organisch-anorganische Hybrid-rotaxaneunclassified

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

et al. 2011

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Mehr als ein Vierteljahrhundert nach der ersten Metalltemplatsynthese eines [2]Catenans in Straßburg existiert nun eine Fülle an Strategien zum Aufbau mechanisch verbundener und verflochtener Strukturen auf molekularer Ebene. Catenane, Rotaxane, Knoten und Borromäische Ringe sind alle erfolgreich über Methoden zugänglich, in denen Metallionen eine Schlüsselrolle spielen. Ursprünglich wurden Metallionen ausschließlich aufgrund ihrer Koordinationschemie verwendet, indem sie entweder die einzelnen Bausteine auf eine Weise anordneten, die durch anschließende Reaktionen die Erzeugung der verschlungenen Produkte ermöglichte, oder indem sie selbst als wesentlicher Bestandteil der Ringe oder als “Stopper” dienten. Vor kurzem wurde die Rolle des Metalls auch auf die Katalyse ausgedehnt: Die Metallionen ordnen die Bausteine nicht nur zu einer verflochtenen oder eingefädelten Struktur an, sondern fördern auch aktiv die Strukturbildung durch kovalenten Einfangen. Dieser Aufsatz fasst die Strategien zur Bildung mechanisch verbundener Molekülstrukturen mit Metallionen zusammen und diskutiert die Taktiken, die zum Aufbau von Überkreuzungen, zur Maximierung der Ausbeuten verschlungener und nichtverschlungener Produkte und zur Bildung eingefädelter oder verflochtener Intermediate durch kovalenten Einfang zur Verfügung stehen.

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Directed 1D Assembly of a Ring‐Shaped Inorganic Nanocluster Templated by an Organic Rigid‐Rod Molecule: An Inorganic/Organic Polypseudorotaxane

Cited by 16 publications

References 29 publications

Strategies and Tactics for the Metal‐Directed Synthesis of Rotaxanes, Knots, Catenanes, and Higher Order Links

Strategies and Tactics for the Metal‐Directed Synthesis of Rotaxanes, Knots, Catenanes, and Higher Order Links

Adsorption and Catalytic Properties of the Inner Nanospace of a Gigantic Ring‐Shaped Polyoxometalate Cluster

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

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