Recent developments in the thiamacrocyclic chemistry of the latter d-block elements

Kim, Seulgi; Lindoy, Leonard F.; Lee, Shim Sung

doi:10.1016/j.ccr.2014.08.011

Cited by 35 publications

(12 citation statements)

References 133 publications

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“…Crown ethers are one of the simplest macrocycle categories and have opened the era of alkali-metal coordination chemistry in synthetic inorganic chemistry. − As well as possessing central cavities, crown ethers have frequently been tuned by substituting their O heteroatoms by N donors to achieve endocyclic recognition (metal-in-cavity, Chart a) of certain metal ions, − while S-containing crown ethers (thiacrowns or thiamacrocycles) often form exocyclic complexes in which metal ions exist outside the cavity (Chart b) because of the electron sufficiency of S donors. − The use of such exocoordination is synthetically attractive for the construction of novel metallosupramolecular entities and coordination networks based on macrocyclic ligand building blocks. − …”

Section: Introductionmentioning

confidence: 99%

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Kim

Park

et al. 2021

Inorg. Chem.

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In the construction of metallosupramolecules, the reaction sequence in a three-reactant system (one ligand plus two metal ions) could be one of the controlling factors influencing the outcome of the reaction. In this work, the formation of supramolecular isomers (1 and 2) and an endo/exocyclic Cu+ complex (4) of the NS4-macrocycle (L) via different sequential metal addition protocols (routes I–III) is reported. In one-pot reactions of L with Cu(CH3CN)4PF6 in the absence (route I) and presence (route II) of CdI2, a cyclic dimer CuI complex, [Cu2(L)2](PF6)2 (1), and a one-dimensional coordination polymer, [Cu2(L)2] n ·n[CdI4] (2), were obtained, respectively. Interestingly, the complex cations in 1 and 2 are supramolecular isomers formed via cyclization and polymerization upon complexation, respectively, probably due to different geometric and electronic complementarities, via the C–H···X– hydrogen bonds, between L and the counterion. In the two-step reaction (route III), an endocyclic Cd2+ complex, [Cd(L)I2] (3), obtained in the first step was utilized in the following reaction with Cu(CH3CN)4PF6, giving rise to an endo/exocyclic tetranuclear Cu+ complex, [Cu4(L)2(CH3CN)6](PF6)4 (4), via Cd2+ → 2Cu+ substitution, which is not accessible by conventional procedures. Solution studies by comparative NMR and electrospray ionization mass spectroscopy also support metal substitution by showing the stronger binding affinity of Cu+ over Cd2+. These results demonstrate that the metal substitution protocol could be useful for reaching novel metallosupramolecules difficult to obtain by other methods.

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Section: Introductionmentioning

confidence: 99%

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Kim

Park

et al. 2021

Inorg. Chem.

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“…In this study, we wished to explore the metal ion-driven chiral inversion of pillar[5]arene via the rational modification of its parent structure because metal ions are an essential factor in particular biosystems. For this, we have proposed a bicyclic pillar[5]-thiacrown ( rac - L , Scheme a) incorporating a fused “thiacrown” because of its propensity for recognizing soft metal ions. − As shown in Scheme c, each of two expected enantiomers ( pS - L and pR - L ) of rac - L has an in–out equilibrium, thus rac - L is expected to have four conformers such as in-pS - L , in-pR - L , out-pS - L , and out-pR - L .…”

Section: Introductionmentioning

confidence: 99%

“…The fused thiacrown has potent metal (M) binding sites via S–M bonds which might induce the metal binding inside ( endo -coordination) or outside ( exo -coordination) the thiacrown (Scheme d). − We previously reported a series of thiacrowns that form diverse types of soft metal complexes depending on the coordination modes. − In our experience, the endo - and exo -coordination modes are conditionally controllable , and this result make them more attractive because of applications in on–off type photophysical chemosensors as well as for understanding the sensing mechanism. − …”

Section: Introductionmentioning

confidence: 99%

pseudo[1]Catenane-Type Pillar[5]thiacrown Whose Planar Chiral Inversion is Triggered by Metal Cation and Controlled by Anion

et al. 2018

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Chiral inversion of single molecules has been a challenging task because chirality information controls structures and functions of various molecules, artificial nanostructures, DNA, and proteins. Herein we present a pseudo[1]catenane-type molecule whose planar chiral inversion is driven by a metal ion under the control of anions for the first time. Considering an in-out equilibrium of a fused thiacrown and the soft metal binding, pillar[5]thiacrown ( rac-L) was synthesized. Two planar-chiral enantiomers of rac-L ( in-pS-L and in-pR-L) were isolated and the absolute configuration was determined by circular dichroism and single crystal X-ray analysis. The in-pS-L recognizes Hg to trigger the chiral inversion to out-pR-L, to our surprise; it takes place only in the presence of ClO or NO among the anions used. In the mercury(II) perchlorate complex solution, anion-exchange from ClO to I or removal of Hg by addition of S makes the system reversible. The crystallographic approach reveals that the anions act as coordination mode-directing species ( endo- or exo-coordination) which play a decisive role on the chiral inversion. For instance, the week coordinating ClO allows Hg to locate inside the thiacrown ( endo-coordination) which causes the chiral inversion from in-pS-L to out-pR-L due to the expansion of the thiacrown unit upon endo-mode complexation. Oppositely, the strong coordinating I takes Hg out of the thiacrown ( exo-coordination) without large conformational changes of the thiacrown, resulting in no chiral inversion. A series of experimental works was also accomplished with the other enantiomer in-pR-L, which afforded identical results. Consequently, the chiral inversion is governed by steric factors that arise from the coordination modes depending on the coordinating ability of anions. This work demonstrates the first chiral inversion induced by combination of metal ion and anion and presents a new perspective on the supramolecular coordination chemistry of pillar[ n]arenes.

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“…[1][2][3][4][5] These include the family of sulfurcontaining macrocycles (thiamacrocycles or thiacrowns), which often exhibit exocyclic coordination (metal binds outside the cavity) owing to electron sufficiency in the valence shell and related steric reasons associated with the sulfur donors. [6][7][8] Indeed, exo-coordination is attractive because it could connect macrocycles in diverse arrangements, allowing the construction of very fascinating network assemblies.…”

Section: Introductionmentioning

confidence: 99%

“…Based on this phenomenon, exo-coordination can serve as a tool for crystal engineering via the use of diverse controlling factors. [6][7][8] Our group have been interested in the architectural control of supramolecular coordination products via the thiamacrocycle platforms. [8] We have established several strategies for the rational synthesis of new types of metallosupramolecules that include not only discrete endo-and exocyclic complexes but also infinite exo-coordinated polymers.…”

Section: Introductionmentioning

confidence: 99%

Endocyclic and Endo–Exocyclic Silver(I) Complexes of Thiaoxaaza Macrocycles: Crystallographic and NMR Studies

Kang

Lee

et al. 2017

Aust. J. Chem.

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A comparative investigation of the coordination behaviour of a 19-membered NO2S2-macrocycle (L1) and a 20-membered NO2S3-macrocycle (L2) is reported. On silver(i) complexation, L1 yields a discrete endocyclic mononuclear complex, whereas L2 affords a one-dimensional coordination polymer in which the endo-coordinated macrocyclic complex units are linked by silver(i) ions outside the cavity via endo–exo-coordination. The larger ring cavity along with the flexible nature of L2 may induce the weaker endocyclic complexation and contribute to exocyclic coordination as well. In NMR titration studies for the corresponding complex system, however, no evidence of exocyclic coordination was observed. Instead, L1 and L2 form a stable endocyclic 1 : 1 silver(i) nitrate complex, with a higher affinity for the former ligand.

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Recent developments in the thiamacrocyclic chemistry of the latter d-block elements

Cited by 35 publications

References 133 publications

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

pseudo[1]Catenane-Type Pillar[5]thiacrown Whose Planar Chiral Inversion is Triggered by Metal Cation and Controlled by Anion

Endocyclic and Endo–Exocyclic Silver(I) Complexes of Thiaoxaaza Macrocycles: Crystallographic and NMR Studies

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Recent developments in the thiamacrocyclic chemistry of the latter d-block elements

Cited by 35 publications

References 133 publications

Influence of the Reaction Sequence on the Complexation of an NS4-Macrocycle with CdII and CuI Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic CuI Complex

Influence of the Reaction Sequence on the Complexation of an NS4-Macrocycle with CdII and CuI Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic CuI Complex

pseudo[1]Catenane-Type Pillar[5]thiacrown Whose Planar Chiral Inversion is Triggered by Metal Cation and Controlled by Anion

Endocyclic and Endo–Exocyclic Silver(I) Complexes of Thiaoxaaza Macrocycles: Crystallographic and NMR Studies

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Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex