Formation of Racemate and Mesocate Complexes from an Achiral Tripodal Ligand Containing Three Benzimidazole Groups

Cai, Yue‐Peng; Su, Cheng‐Yong; Chen, Chun‐Long; Li, Yue‐Ming; Kang, Byeong‐Cheol; Chan, and Albert S. C.; Kaim, Wolfgang

doi:10.1021/ic025934y

Cited by 51 publications

(7 citation statements)

References 35 publications

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“…Our previous investigations using linear quinoline or benzimidazole-based polydentate ligands with flexible spacers resulted in a broad range of structures including helicates, − polymeric 2D networks, and metallacycles, while, in contrast, N , N ‘-bipyridyl-based rigid ligands only resulted in multidimensional polymeric networks . Interestingly, by the careful design of semirigid ligands containing aromatic cores and benzimidazolyl (Bim) ring arms, we were able to construct both rectangular or prismatic architectures 22 and two-dimensional networks .…”

Section: Introductionmentioning

confidence: 95%

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI₂ and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

et al. 2003

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The reactions of HgI(2) with the semirigid ditopic ligand 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bbimms) afforded three new complexes, [Hg(2)(mu-I)(2)I(2)(bbimms)] (1), [Hg(2)I(4)(bbimms)(2)] (2), and catena-poly[HgI(2)(bbimms)] (3). The ligand and all complexes have been structurally characterized by single-crystal X-ray diffraction. 1 is a triply bridged dinuclear complex comprised of two Hg(II) ions, one bridging ligand, two bridging I(-) anions, and two terminal I(-) anions. 2 is a dinuclear metallamacrocycle comprised of two Hg(II) ions, two bridging ligands, and four terminal I(-) anions, while 3 is a helical chain with the repeating unit of HgI(2)(bbimms). 2 and 3 can be classified as supramolecular isomers, and both are related to the triply bridged precursor 1 via the addition of one more ligand in a ring-opening process.

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Section: Introductionmentioning

confidence: 95%

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI₂ and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

et al. 2003

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“…The most remarkable structural feature of complexes 2 and 4 is their double‐propeller‐type topology, which originates from the independent propeller‐type orientation of the achiral tripodal ntbi ligands. Such an arrangement is inherently chiral and is able to induce chirality in the complexes (Scheme ) . However, as two face‐to‐face tripodal ligands are present in one complex, the mutual propeller orientations of the two ligands decide the overall chirality.…”

Section: Resultsmentioning

confidence: 99%

Tuning the Magnetoluminescence Behavior of Lanthanide Complexes Having Sphenocorona and Cubic Coordination Geometries

et al. 2016

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Abstract:The reaction of the tripodal fluorophoric ligand tris(benzimidazol-2-ylmethyl)amine (ntbi) with two different lanthanide salts [Ln(NO 3 ) 3 and LnCl 3 (Ln = Dy, Ho, Tb)] afforded two new classes of mononuclear complexes. The class 1 complexes [{Ln(ntbi)(NO 3 ) 3 } 2 ·3CH 3 OH; Ln = Dy (1) and Ho (3)] exhibit very rare "sphenocorona" coordination geometries around the Ln centers, whereas the class 2 complexes [{Ln(ntbi) 2 } 5 · 15Cl·xH 2 O; Ln = Dy, x = 18 (2) and Ln = Tb, x = 27 (4)] show

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“…Two possible architectures can be obtained according to the coupling of the chiral centers: homochiral helicates with ΔΔ or ΛΛ configuration and achiral mesocates with ΔΛ configuration. In most cases, racemic mixtures of helicates are the preferred products, while the formation of mesocates is far less common. − A great deal of effort has been dedicated to controlling the formation of helicates versus mesocates. Albrecht and Kotila found that the length of an alkyl spacer between two chelating moieties plays an important role in the diastereoselectivity.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Pentanuclear Mesocate versus Octanuclear Helicate: Size Effect of the [M^II₃(μ₃-O/X)]ⁿ⁺ Triangle Core

Bao

Liu

et al. 2012

Inorg. Chem.

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The first cluster mesocate (H(3)O)[{Fe(2)(μ-L)(3)}{Fe(3)(μ(3)-O)(μ-Cl)(3)}]·3EtOH (1) and a new series of cluster helicates, [{Mn(μ-L)(3)}(2){Mn(3)(μ(3)-Cl)}(2)](ClO(4))(2)·2MeOH·6H(2)O (2), [{Cd(μ-L)(3)}(2){Cd(3)(μ(3)-Br)}(2)]Br(2)·2DMF·14H(2)O (3), and [{Cd(μ-L)(3)}(2){Cd(3)(μ(3)-I)}(2)](CdI(4))·3H(2)O (4), have been synthesized by the self-assembly of a C(2)-symmetric tritopic ligand, 2,6-bis[5-(2-pyridinyl)-1H-triazol-3-yl]pyridine (H(2)L) with different metal halogen salts. Single-crystal X-ray diffraction and electrospray ionization mass spectrometry measurements were carried out on these complexes. 1 was crystallized as a triple-stranded pentanuclear mesocate in which a [Fe(II)(3)(μ(3)-O)](4+) triangle core was wrapped by a [Fe(II)(2)(μ-L)(3)](2-) shell. 2-4 have similar octanuclear helicate structures in which two propeller-shaped [M(II)(μ-L)(3)](4-) units embrace two [M(II)(3)(μ(3)-X)](5+) triangles inside. The [M(II)(3)(μ(3)-O/X)](n+) triangle core were found to play an important role in the selective synthesis of the two architectures: the smaller [Fe(II)(3)(μ(3)-O)](4+) triangle core prefers a mesocate structure because it matches the small cavity imposed by the [Fe(II)(2)(μ-L)(3)](2-) shell, while the bigger [M(II)(3)(μ(3)-X)](5+) induces a screwed arrangement of the ligands, thus stabilizing the helicate structure. Variable-temperature magnetic susceptibility measurements indicate that both 1 and 2 display an overall antiferromagnetic coupling. Density functional theory calculations for 1 confirm the strong antiferromagnetic interaction in the central [Fe(II)(3)(μ(3)-O)](4+), while interaction through the triazole bridging ligands is slightly ferromagnetic. For 2, three interaction pathways were considered and all sets of J values reveal the presence of weak antiferromagnetic interaction.

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Formation of Racemate and Mesocate Complexes from an Achiral Tripodal Ligand Containing Three Benzimidazole Groups

Cited by 51 publications

References 35 publications

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI₂ and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI₂ and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

Tuning the Magnetoluminescence Behavior of Lanthanide Complexes Having Sphenocorona and Cubic Coordination Geometries

Self-Assembly of Pentanuclear Mesocate versus Octanuclear Helicate: Size Effect of the [M^II₃(μ₃-O/X)]ⁿ⁺ Triangle Core

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Formation of Racemate and Mesocate Complexes from an Achiral Tripodal Ligand Containing Three Benzimidazole Groups

Cited by 51 publications

References 35 publications

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI2 and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI2 and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

Tuning the Magnetoluminescence Behavior of Lanthanide Complexes Having Sphenocorona and Cubic Coordination Geometries

Self-Assembly of Pentanuclear Mesocate versus Octanuclear Helicate: Size Effect of the [MII3(μ3-O/X)]n+ Triangle Core

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Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI₂ and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

Formation of Dinuclear, Macrocyclic, and Chain Structures from HgI₂ and a Semirigid Benzimidazole-Based Bridging Ligand: An Example of Ring-Opening Supramolecular Isomerism

Self-Assembly of Pentanuclear Mesocate versus Octanuclear Helicate: Size Effect of the [M^II₃(μ₃-O/X)]ⁿ⁺ Triangle Core