A deep tetranuclear metallo-cavitand with bis(aryl) palladium bridges

Botana, Enrique; Lubinu, M. Caterina; Silva, Eric Da; Espinet, Pablo; Mendoza, Javier de

doi:10.1039/c0cc00534g

Cited by 6 publications

(4 citation statements)

References 20 publications

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“…With the success in structural evaluation of series of cavitands, we eventually set out to study the diastereomeric ratios that result from epoxidation of allylsilanes rac ‐ 2 – rac ‐ 11 . The results are summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

Inherently Chiral Cavitand Curvature: Diastereoselective Oxidation of Tethered Allylsilanes

et al. 2019

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Syntheses of inwardly and outwardly directed allylsilanes those are tethered to new inherently chiral cavitands are described. Oxidized with mCPBA, these allylsilanes result in diastereomeric mixtures of epoxide molecules. Thus, it enables us to have comparative study of cavitand‐structure diastereoselectivity relationship, which revealed that an inward allylsilane group flanked by a dibenzo[f, h]quinoxaline and two bridged methylene groups have the best chemical yield and diastereoselection.

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Section: Resultsmentioning

confidence: 99%

Inherently Chiral Cavitand Curvature: Diastereoselective Oxidation of Tethered Allylsilanes

et al. 2019

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“…The resulting structure is able to encapsulate other calix [4]arenes as guests, with NMR titrations at low temperature indicating that entropy plays a key role in guest binding. 19 The weak binding of a series of aromatic cyano guests within the paddle-wheel like structure of [Pd 2 (L 30 ) 4 ] has also been described. 20 The [2 + 2] photoadditions and [2 + 4] Diels-Alder cycloadditions of aceanthrylene, 1, and 1H-cyclopenta[l]phenanthrene, 2, with N-cyclohexylmaleimide, 3, in the presence of both [(en) 6 Pd 6 (L 31 ) 4 ] 12+ and [(en*) 6 Pd 6 (L 31 ) 4 ] 12+ have been described.…”

Section: Cagesmentioning

confidence: 99%

“…11 Nanofibers of these metallocycles were generated by diffusing hexane into homogeneous solutions of both. The self-sorting behaviour of the six-component library consisting of two substituted phen ligands, L 15 and L 16 , unsubstituted phen and terpy ligands, Cu and Zn, which gives just two complexes, [(L 15 )(terpy)Zn] 2+ and [(L 16 )(phen)Cu] + , from a possible twenty, has been used to prepare an isosceles triangular species from building blocks L 17 -L 19 . 12 In a related report, the same six-component library has been extended to eight by the inclusion of [(L 20 )Zn] and L 21 , which similarly self-sorts to give just three complexes, [(L 15 )(terpy)Zn] 2+ , [(L 16 )(phen)Cu] + and [(L 20 )(L 21 )Zn], from a possible thirty five.…”

Section: Cyclic Oligomers (Metallocycles)mentioning

confidence: 99%

“…12 In a related report, the same six-component library has been extended to eight by the inclusion of [(L 20 )Zn] and L 21 , which similarly self-sorts to give just three complexes, [(L 15 )(terpy)Zn] 2+ , [(L 16 )(phen)Cu] + and [(L 20 )(L 21 )Zn], from a possible thirty five. 13 By incorporating these library member components into building blocks L 19 , L 22 and L 23 , the first example of a scalene triangular assembly has been realised.…”

Section: Cyclic Oligomers (Metallocycles)mentioning

confidence: 99%

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Supramolecular coordination chemistry

Lusby¹

2011

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews the literature reported during 2010 in the field of supramolecular coordination chemistry. With a few exceptions, this review has been limited to discrete assemblies, and as such will not describe metallosupramolecular coordination polymers or metallo-organic frameworks. HighlightsHighlights for 2010 include the self-assembly of a M 24 L 48 rhombicuboctahedron and the emergence of criticallity switching between this and the smaller M 12 L 24 cuboctahedron, 43 a molecular double-ball bearing, 49 an actuator prototype, 72 and polymer growth regulation by a triple-decker, allosterically regulated metallosupramolecular catalyst.

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Capsule–Capsule Conversion by Guest Encapsulation

et al. 2016

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Guest-induced M 18 L 6 -M 24 L 8 capsule-capsule conversion is reported. Both capsules are composed of Pd II ethylenediamine units (M) and 1,3,5-tris(3,5-pyrimidyl)pyrimidine (L), and form trigonal bipyramidal (M 18 L 6 )a nd octahedral (M 24 L 8 )c losed-shell structures with huge hydrophobic inner spaces.T he M 18 L 6 trigonal bipyramid is converted to the M 24 L 8 octahedron through encapsulation of large aromatic guests,w ith the latter capsule possessing ac avity volume three times larger than the former.Despite the dynamic properties of the capsule host, the encapsulated guests are difficult to extract and are thus isolated from the external environment.Molecular capsules show unique host properties that are different from those of other synthetic hosts in that they possess isolated nanocavities that allow the properties and reactivities of encapsulated guests to be maintained.[1] Recently,al ot of effort has been put into constructing capsular structures of ever-increasing size, [2] but relatively few of these capsules show distinct guest-binding properties in their large cavities,t hus demonstrating that simple cavity expansion does not automatically lead to large guest encapsulation. We have previously reported trigonal bipyramidal M 18 L 6 coordination capsule 1a,b ut, unlike similar M 6 L 4 open cages that bind various organic guests in their cavities, [3] capsule 1a did not show any encapsulation behavior toward organic guests in water.[2b] We assumed that, in addition to the open framework, the highly electron-deficient environment of the M 6 L 4 cages offered by the metal-coordinated tris(4-pyridyl)triazine ligand is essential for guest binding.W etherefore redesigned the panel ligand of capsule 1a to give am ore electrondeficient 1,3-pyrimidine-cored panel, and created the more electron-deficient M 18 L 6 capsule 1b.H erein, we report that capsule 1b does indeed encapsulate large guests and, unexpectedly and surprisingly,t he large guest encapsulation triggers the conversion of M 18 L 6 capsule 1b into cavityexpanded M 24 L 8 octahedral capsule 2b (Figure 1). This guesttriggered M 18 L 6 -M 24 L 8 switch presents ar are example of capsule-capsule conversion with concurrent dramatic cavity expansion. [4] By simply mixing [(en)Pd(ONO 2 ) 2 ]( 3;e n= ethylenediamine) and our new ligand 2,4,6-tris(3,5-pyrimidyl)pyrimidine (4)i nw ater, trigonal bipyramidal M 18 L 6 coordination capsule 1b was obtained. Amixture of 3 (34.9 mg, 120 mmol) and 4 (12.6 mg, 40 mmol) was stirred in D 2 Osolution at 70 8 8C for 24 h, and the 1 HNMR spectrum after the complexation clearly showed the formation of as ingle product with panel ligand 4 placed in a C 2v environment. Six aromatic signals were observed in a1:2:2:2:2:1 integral ratio (Figure 2a), thus suggesting that 3 and 4 were assembled into trigonal bipyramid 1b with D 3h symmetry and am irror plane (s h ) vertical to the main apical C 3 axis.T here are many possible isomers of this M 18 L 6 capsular structure because ligand 4 does not have a C 3 symmetr...

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A deep tetranuclear metallo-cavitand with bis(aryl) palladium bridges

Abstract: A neutral metallo-cavitand based on cis bis-perhaloaryl Pd(II) bridges co-ordinated at the corners of a deep calix[4]arene. Both the metallo-cavitand and its inclusion complexes with other calix[4]arenes were investigated by means of (1)H and (19)F NMR experiments.

Cited by 6 publications

References 20 publications

Inherently Chiral Cavitand Curvature: Diastereoselective Oxidation of Tethered Allylsilanes

Inherently Chiral Cavitand Curvature: Diastereoselective Oxidation of Tethered Allylsilanes

Supramolecular coordination chemistry

Capsule–Capsule Conversion by Guest Encapsulation

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