Oligo-β-diketones as versatile ligands for use in metallo-supramolecular chemistry: Recent progress and perspectives

Clegg, Jack K.; Li, Feng; Lindoy, Leonard F.

doi:10.1016/j.ccr.2021.214355

Cited by 26 publications

(29 citation statements)

References 111 publications

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“…Synthesis and crystal structures of [AgL 2 ][X] complexes with L = bpy, dmbpy, Brdmbpy, phen, dmphen (X = ClO À , BF 4 À , PF 6 À )…”

Section: Resultsmentioning

confidence: 99%

“…The systematic exploitation of metal-ligand coordination bonds for preparing sophisticated (supra)molecular architectures under thermodynamic control such as cages, grids and clusters, [1][2][3][4] nanostructures [5][6][7][8] or entangled rotaxanes, catenates and knots [9][10][11][12] during the last three decades finds its origin in the seminal report of the spontaneous assembly of doublestranded helicates from oligobipyridine ligands and copper(I) [13] or silver(I) [14] cations by Lehn and co-workers (Figure 1). [15] The diamagnetic character of these closed-shell d 10 cations greatly helped in the original characterization of their complexes in solution by NMR spectroscopic techniques, whereas their preferences for soft bidentate chelating ligands make them ideal for working as crucial partners in the design of multi-diimine helicates, [16][17][18] grids, catenates and knots.…”

Section: Introductionmentioning

confidence: 99%

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Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′‐Diimine Ligands

Zare

Piguet

Prescimone

et al. 2022

Chemistry A European J

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The allosteric positive cooperativity accompanying the formation of compact [Cu I (α,α'-diimine) 2 ] + building blocks contributed to the historically efficient synthesis of metalcontaining catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen-resistant [Ag I (α,α'-diimine) 2 ] + units in modern entangled metallosupramolecular assemblies, a related thermodynamic justification was absent. Solid-state structural characterizations show the successive formation of [Ag I (α,α'-diimine)(CH 3 CN)][X] and [Ag I (α,α'-diimine) 2 ][X] upon the stepwise reactions of α,α'diimine = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives with AgX (X = BF 4 À , ClO 4 À , PF 6 À ). In room-temperature, 5-10 mM acetonitrile solutions, these cationic com-plexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (= noncooperative) binding of two successive bidentate ligands around Ag I , a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6' positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag-(dmbpy) 2 ] + and [Ag(dmphen) 2 ] + , a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy) 2 ] + further reinforces the positively cooperative process, while limiting the overall decrease in metal-ligand affinity.

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“…Synthesis and crystal structures of [AgL 2 ][X] complexes with L = bpy, dmbpy, Brdmbpy, phen, dmphen (X = ClO À , BF 4 À , PF 6 À )…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′‐Diimine Ligands

Zare

Piguet

Prescimone

et al. 2022

Chemistry A European J

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“…Moreover, β-diketones chelate uncharged bidentate ligands, which possess such advantages as a monovalent negatively charged binding site, which results in the formation of neutral 3:1 ligand-lanthanide luminescent complexes [54]. The photophysical properties of lanthanide-β-diketonate complexes have been widely investigated [55][56][57].…”

Section: Introductionmentioning

confidence: 99%

Cross-Linked Luminescent Polymers Based on β-Diketone-Modified Polysiloxanes and Organoeuropiumsiloxanes

et al. 2022

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Nowadays, luminescent materials attract wide attention due to their valuable characteristics and broad area of potential application. Luminescent silicone-based polymers possess unique properties, such as flexibility, hydrophobicity, thermal and chemical stabilities, etc., which allow them to be utilized in various fields, such as optoelectronics, solid-state lasers, luminescent solar concentrators, sensors, and others. In the present work, a metal-ligand interaction approach was applied to obtain new cross-linked luminescent polymers based on multiligand polysiloxanes with grafted β-diketone fragments and organoeuropiumsiloxanes containing various organic substituents. Organoeuropiumsiloxanes were utilized as a source of Eu3+ ions due to their compatibility with the silicon matrix. All synthesized polymers were fully characterized and their physicochemical, mechanical, self-healing, optical, and thermal properties were studied.

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“…37 These helicates are self-assembled starting from achiral bis-β-diketone ligands. Oligo-β-diketones are versatile ligands for the preparation of metallo-supramolecular architectures 38,39 ranging from metallocycles, cages and MOFs, [40][41][42][43][44] to helicates 37,[45][46][47] and even to interlocked structures. [48][49][50] Herein, by using a close related bis-β-diketone ligand, we present a larger series of seven [Ln2L4] 2− quadruple-stranded helicates (Ln = La, Nd, Eu, Tb, Er, Tm and Lu), Figure 1, that once assembled undergo transmetalation.…”

Section: Introductionmentioning

confidence: 99%

Dynamic lanthanides exchange between quadruple-stranded cages: effect of ionic radius differences on kinetics and thermodynamics

Rancan

Rando

Bosi

et al. 2022

Preprint

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Seven different [Ln2L4]2− (Ln = La, Nd, Eu, Tb, Er, Tm and Lu) lanthanide-based quadruple-stranded helicates are here reported and transmetalation among pre-assembled cages was studied. Combining two homonuclear helicates [LnA2L4]2− and [LnB2L4]2− leads to the formation of a mixture of homo- and heteronuclear systems due to ion exchange. This dynamic behaviour was studied by electrospray ionization mass spectrometry (ESI-MS) both qualitatively and quantitatively allowing to gain information on the thermodynamics as well as on the kinetics of the process. The rate of the Ln ion exchange is strongly dependent on the difference in lanthanide effective ionic radius (ΔEIR). Upon increasing ΔEIR, the kinetic constants grow exponentially: from the minimum to the maximum value of ΔEIR, the kinetic constants of the forward and backward reactions increase by three orders of magnitude. On the contrary, the equilibrium constant is the same for all the [LnA2L4]2−/[LnB2L4]2− couples, showing that the transmetalation is mainly entropy-driven towards a statistical mixture and not affected by ΔEIR.

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Oligo-β-diketones as versatile ligands for use in metallo-supramolecular chemistry: Recent progress and perspectives

Cited by 26 publications

References 111 publications

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′‐Diimine Ligands

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′‐Diimine Ligands

Cross-Linked Luminescent Polymers Based on β-Diketone-Modified Polysiloxanes and Organoeuropiumsiloxanes

Dynamic lanthanides exchange between quadruple-stranded cages: effect of ionic radius differences on kinetics and thermodynamics

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