The synthesis and structural characterization of a novel tetracobalt cluster of 5,6,11,12,17,18-hexadehydrotribenzo[a,e,i]-cyclododecine

Djebli, Abdellah; Ferrara, Joseph D.; Tessier‐Youngs, Claire; Youngs, Wiley J.

doi:10.1039/c39880000548

Cited by 21 publications

(16 citation statements)

References 2 publications

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“…The works featured herein serve as tangible examples of both the exciting outlook and practical limitations of AEM chemistry in materials applications. Versatile hosting of metal ions, [5][6][7][8] aryl derivatives, [13][14][15][16][17] saccharides, 14 and fullerenes 15,16 speaks to AEM potential in chemical sensing, while laying the foundation for the preparation of molecularly resolved host/ guest coordination materials. Weak binding interactions may be overcome by the introduction of heterocyclic binding sites, or by the use of electron donating or withdrawing substituents to modulate AEM electronics.…”

Section: Discussionmentioning

confidence: 99%

“…5 This inclusion complex is of interest in molecular electronics, due to the desirable coordination between a soft donor atom and a conjugated acceptor. Complexes of the parent o-AEM with Cu(I) 6 and Co(0) 7 have also been characterized (although their geometries are different from Ni(0) complex). Larger metals, such as Ag(I), cannot fit into the center of a single macrocycle and thus form a sandwich complex wherein the metal is squeezed between two macrocycles.…”

Section: Aems As Supramolecular Hostsmentioning

confidence: 99%

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Arylene ethynylene macrocycles: from molecular hosts to components of high-performance supramolecular architectures

Smith

Miljanić

2015

Org. Biomol. Chem.

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Supramolecular chemistry of conjugated and conformationally rigid arylene ethynylene macrocycles (AEMs) has been the subject of increasing recent interest. AEMs are suited to function as supramolecular building blocks and hosts for small molecular guests thanks to their well-defined, non-collapsible central cavities and the potential for long range ordering through intermolecular π-stacking. Their syntheses are highly modular--albeit typically lengthy--allowing access to a great structural variety of AEM candidates for applications as carbon-rich mesogens and ligands in liquid crystals, nanoporous solids, molecular electronics, and chemical sensors. In this perspective, we highlight our recent work on the inclusion complexes and porous materials constructed from AEMs. Through this prism, we reflect on the recent advances and the remaining challenges in the supramolecular chemistry of AEMs.

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Section: Discussionmentioning

confidence: 99%

Section: Aems As Supramolecular Hostsmentioning

confidence: 99%

Arylene ethynylene macrocycles: from molecular hosts to components of high-performance supramolecular architectures

Smith

Miljanić

2015

Org. Biomol. Chem.

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“…A view down the b axis ( Figure 3) shows a herringbone pattern with an interplanar distance of 3. 35 (1) A. The crystal structure of TBC shows the molecules are also slipped stacked12 with an interplanar spacing of 3.29 8, and the benzo groups staggered.…”

Section: -207mentioning

confidence: 99%

Synthesis and structural and theoretical characterization of a nickel(0) complex of tribenzocyclyne (TBC) and the preparation of a novel organometallic conductor

Ferrara¹,

Tanaka²,

Fierro³

et al. 1989

Organometallics

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Reaction of Ni(COD)2 with TBC in benzene affords a planar nickel(0) complex, Ni(TBC), with the nickel atom coordinated equally by all three alkynes of the TBC ligand. The complex crystallizes in the noncentrosymmetric space group Pna21 with a = 15.518 (3) A, b = 18.761 (4) A, c = 5.375 (1) A, V = 1564.8 (5) A3, and 2 = 4. The nickel-carbon and carbon-carbon (alkyne) bond lengths average 1.958 (5) and 1.240 (10) A, respectively. The molecules are slipped-stacked in an eclipsed conformation with an interplanar spacing of 3.35 (1) A. The reaction chemistry of Ni(TBC) with several small molecules including H20, CDC13, CO, COz, 02, and CH&N has been explored. The rates of reaction with CO and O2 are solventdependent. Electrochemical studies of Ni(TBC) and TBC show two reduction waves which are moderately reversible. ASED-MO calculations on Ni(TBC) indicate the HOMO is primarily metal centered, whereas the LUMO is ligand centered. Ni(TBC) is reduced with lithium, sodium, and potassium in various solvents (THF and DME) in the presence of various chelating agents (TMEDA, 18-crown-6, and cryptand-(2.2.2)) to the monoanion and dianion. The material [K(C222)I2[Ni(TBC)] was combined with Ni(TBC) to yield a conducting material. The maximum conductivity (via two-probe powder compaction) was observed to be 2 X (a cm)-' at 0.5 electron per Ni(TBC) unit. A parallel study on TBC showed a maximum conductivity of 8 (2) X 10" (a cm)-' at 0.6 electron per TBC unit. IntroductionTransition-metal complexes of planar metallomacrocycles, including ligand systems such as the porphyrins' and phthalocyanines,2 have been studied in depth as precursors for one-dimensional conductors. These complexes have several key features in common: the molecules are planar with an extended mystem, the ligand atoms which complex the metal are relatively hard nitrogen donors, the ligand has a formal negative oxidation state, and

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“…In particular, a variety of organometallic species in which the p electron-rich 8 participates as the ligand have been prepared. Treatment of 8 with Co 2 (CO) 8 furnished the 66-electon cluster 69, which was characterized by X-ray crystallography [30]. The authors inferred that the binding of cobalt to the macrocycle resembled the postulated transition state of a metalmediated [2+2+2] cyclotrimerization of alkynes.…”

Section: Comparison Of the Two Pathwaysmentioning

confidence: 99%

Macrocycles Based on Phenylacetylene Scaffolding

Jones

O’Connor

Haley

2004

Acetylene Chemistry

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The synthesis and structural characterization of a novel tetracobalt cluster of 5,6,11,12,17,18-hexadehydrotribenzo[a,e,i]-cyclododecine

Abstract: The interaction of octacarbonyldicobalt with 5,6,11 ,I 2,17,18-hexadehydrotribenzo[a,e,~~cyclododecine (tbc) yields the sixty-six electron cluster Co4(tbc)(CO), whose structure may model the transition state during metal catalysed [2 + 2 + 2]cyclotrimerization of alkynes.

Cited by 21 publications

References 2 publications

Arylene ethynylene macrocycles: from molecular hosts to components of high-performance supramolecular architectures

Arylene ethynylene macrocycles: from molecular hosts to components of high-performance supramolecular architectures

Synthesis and structural and theoretical characterization of a nickel(0) complex of tribenzocyclyne (TBC) and the preparation of a novel organometallic conductor

Macrocycles Based on Phenylacetylene Scaffolding

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