A (3,6)-connected layer with an unprecedented adeninate nucleobase-derived heptanuclear disc

Liu, Zhengyu; Zhang, Hongyun; Yang, En‐Cui; Zhao, Xiao‐Jun

doi:10.1039/c4dt04020a

Cited by 15 publications

(11 citation statements)

References 54 publications

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“…In general, heptanuclear oxo‐copper clusters are known to appear as disk‐shaped units in adenine/hydroxide, tartrate/hydroxide, 7‐azaindole/hydroxide or Schiff base mixtures. These complexes exhibit ferro‐,, ferri‐ and antiferromagnetic, , behavior. At the same time, previously reported complexes significantly differ from compounds 1 and 2 in the mutual disposition and connectivity of metal atoms and bridging groups.…”

Section: Resultsmentioning

confidence: 99%

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

et al. 2018

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Two prismatic phenyl-(PhSiO 1.5 ) 14 (CuO) 7 (1, 29 % yield) and methyl-(MeSiO 1.5 ) 14 (CuO) 7 (2, 19 % yield) heptacoppersilsesquioxanes were obtained by the interaction of Cu,Na-based cage silsesquioxanes [(RSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 ] (R = Ph, Me) with 4,4′-bipyridine and pyrazine, respectively, acting as "silent witness" ligands. Unusual molecular topologies of both compounds 1 and 2, which are the first representatives of [a] Nesmeyanov Institute of Organoelement Compounds,

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Section: Resultsmentioning

confidence: 99%

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

et al. 2018

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“…The heptameric entity is analogous to that found in the crystalline structures of the compounds [Cu 7 (μ-ade) 6 (μ 3 -OH) 6 (μ-H 2 O) 6 ](NHEt 3 ) 2 (SO 4 ) 2 · n H 2 O ( n = 23, 42) 4 and [Cu 7 (μ-ade) 6 (μ 3 -OH) 6 (μ-H 2 O) 6 ](NO 3 ) 2 ·6H 2 O 20 and resembles that present in the compound 2D-{[Cu 7 (μ-ade) 2 (μ 3 -OH)(μ-sip) 2 (μ-H 2 O) 6 ]·2.5H 2 O} n where four of the adeninate bridges are replaced by two 5-sulphoisophthalate anions …”

Section: Resultsmentioning

confidence: 61%

“…All the metal centers present an octahedral geometry with the usual Jahn−Teller tetragonal elongation (Table S1 of Supporting Information), which is more pronounced for the peripheral copper(II) centers because of the rigidity of the heptanuclear entity. The elongation at the peripheral copper atoms takes place along the metal−water coordination bonds, 21 The use of water as a solvent hinders the presence of direct hydrogen bonding interactions between the adeninato ligands. As a consequence, the crystal structure is dominated by π−π stacking interactions.…”

Section: Structural Description Of [Cumentioning

confidence: 99%

Porous Supramolecular Architectures Based on π-Stacking Interactions between Discrete Metal-Adenine Entities and the Non-DNA Theobromine/Caffeine Nucleobases

Pascual-Colino

Beobide

Castillo

et al. 2018

Crystal Growth & Design

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This work is aimed at the analysis of the π−π stacking interactions as the driving force to develop porous supramolecular metal−organic frameworks (SMOFs) as an alternative to more directional hydrogen bonding interactions. Four compounds based on the interaction between rigid copper/ adenine entities and theobromine/caffeine molecules have been synthesized: [Cu 7 (μ-ade) 4). The blue compound 1 is formed by wheel-shaped cationic heptameric units where the copper atoms are bridged by hydroxide anions, water molecules, and adeninato ligands with a μ-κN3:κN9 coordination mode. The assembly of the heptameric entities and the theobrominate anions takes place mainly through π−π stacking interactions involving the adeninato ligands and theobrominate moieties. Although compound 1 exhibits an open-framework with voids representing 37% of the unit cell, the plasticity of the π−π interactions causes a reversible shrinkage of the porous system upon activation that precludes the adsorption of gas molecules. Dark purple compounds 2−4 contain neutral windmill units in which two copper atoms are bridged by four μ-κN3:κN9 adeninato ligands. Their final crystal structure highly depends on the supramolecular interactions of the theobromine and caffeine molecules. In compound 2, two theobromine molecules are hydrogen bonded to the Hoogsteen face of two trans-arranged adeninato ligands, whereas a third theobromine molecule is joined to the Watson−Crick face of one of the previous adeninato ligands. In compound 3, with a lower amount of theobromine, the Watson−Crick interaction is not present. In both compounds, the three-dimensional (3D) crystal structure requires the additional presence of π−π stacks between the theobromine molecules. In compound 4, as the methyl groups of the caffeine molecule do not allow hydrogen bond interactions, the adeninato ligands are hydrogen bonded among them to generate, together with π-stacking interactions, two-dimensional supramolecular sheets containing rectangular windows in which the caffeine molecules are located. Only compound 4 showed permanent porosity, adsorbing a significant amount of CO 2 (0.88 mmol of CO 2 /g at 5 bar and 273 K). The magnetic characterization of these compounds indicates a ferrimagnetic behavior for 1 and strong intradimeric antiferromagnetic interactions in compounds 2 and 4.

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“…A growing number of {M 7 } clusters with disk‐shaped configurations have been discovered. In our literature survey, we found 41 {M 7 } compounds with disk‐shaped cores . Table listed the formulas, supporting ligands, M II ··· M II distances, and magnetic properties of these clusters.…”

Section: Resultsmentioning

confidence: 99%

Five Disk‐Shaped {M^II₇} (M = Mn, Fe, Co, Cu, Zn) Clusters and One Capsule‐Like {Cu^II₆Na^I₂} Cluster Assembled from the Same Schiff Base Ligand

Zhang

et al. 2016

Eur J Inorg Chem

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Six transition‐metal clusters of compositions [Mn7L6](NO3)2·2CH3OH (1), [Fe7L6](NO3)2·2CH3OH (2), [Co7L6](NO3)2·2CH3OH (3), [Cu7L6](NO3)2 (4), [Zn7L6](NO3)2·2CH3OH (5), and [Cu6Na2L6](NO3)2·4CH3OH (6) {H2L = 2‐(2‐hydroxy‐3‐methoxybenzylideneamino)phenol} have been synthesized under solvothermal conditions. The structures of 1–6 have been established based on single‐crystal X‐ray diffraction studies. Complexes 1–5 possess disk‐shaped {MII7} cores, with the central MII ion and the six peripheral MII ions being linked by six µ3‐O atoms. The six MII ions of the rim of the disk are bridged in a pairwise manner by six µ2‐O atoms. Complex 2 is a very rare example of a disk‐shaped {Fe7} cluster in which all of the Fe atoms exhibit +2 oxidation state. Furthermore, this is the first time that the five isostructural heptanuclear clusters were constructed by using an identical Schiff base ligand. The molecule of complex 6 contains a capsule‐like {Cu6Na2} core. In this core, two sodium ions reside on the two vertices of the capsule and the 12 vertices of the {Cu6O6} hexagonal prism are occupied by alternately arrayed six CuII ions and six O atoms. Photoluminescence studies suggest strong emission for 5 in the solid state at room temperature. Variable‐temperature dc magnetic susceptibility studies were carried out on polycrystalline samples of 1–4 and 6. The ac susceptibility studies were also performed with 3. Strong out‐of‐phase, χ′′, signals were observed for 3 at zero field, suggesting that 3 is a class of single molecule magnet (SMM).

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A (3,6)-connected layer with an unprecedented adeninate nucleobase-derived heptanuclear disc

Abstract: A (3,6)-connected layer with an adeninate nucleobase-derived Cu(II)7 disc was reported, in which six spin-parallel Cu(II) ions in the exterior of the disc are antiferromagnetically coupled with the central one to give an S = 5/2 ground-state.

Cited by 15 publications

References 54 publications

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Porous Supramolecular Architectures Based on π-Stacking Interactions between Discrete Metal-Adenine Entities and the Non-DNA Theobromine/Caffeine Nucleobases

Five Disk‐Shaped {M^II₇} (M = Mn, Fe, Co, Cu, Zn) Clusters and One Capsule‐Like {Cu^II₆Na^I₂} Cluster Assembled from the Same Schiff Base Ligand

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A (3,6)-connected layer with an unprecedented adeninate nucleobase-derived heptanuclear disc

Abstract: A (3,6)-connected layer with an adeninate nucleobase-derived Cu(II)7 disc was reported, in which six spin-parallel Cu(II) ions in the exterior of the disc are antiferromagnetically coupled with the central one to give an S = 5/2 ground-state.

Cited by 15 publications

References 54 publications

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Porous Supramolecular Architectures Based on π-Stacking Interactions between Discrete Metal-Adenine Entities and the Non-DNA Theobromine/Caffeine Nucleobases

Five Disk‐Shaped {MII7} (M = Mn, Fe, Co, Cu, Zn) Clusters and One Capsule‐Like {CuII6NaI2} Cluster Assembled from the Same Schiff Base Ligand

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Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Heptanuclear Cage Cu^II‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Five Disk‐Shaped {M^II₇} (M = Mn, Fe, Co, Cu, Zn) Clusters and One Capsule‐Like {Cu^II₆Na^I₂} Cluster Assembled from the Same Schiff Base Ligand