Templated synthesis of interlocked macrocyclic ligands, the catenands. Preparation and characterization of the prototypical bis-30 membered ring system

Dietrich‐Buchecker, Christiane; Sauvage, Jean‐Pierre

doi:10.1016/s0040-4020(01)85433-8

Cited by 238 publications

(162 citation statements)

References 26 publications

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“…The catenates reported in this work were prepared following our previously reported synthetic strategy based on the combination of Sauvage's Cu(I) template approach [13][14][15][16] 6 ] in acetonitrile was added to it. The reaction mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere.…”

Section: Synthesismentioning

confidence: 99%

“…7 One approach that provides a suitable arrangement of the chromophores is the use of mechanically interlocked rotaxanes and catenanes with attached electron donors and electron acceptors. [8][9][10][11][12] Sauvage's Cu(I) template synthesis [13][14][15][16][17] assures a rigid structure of the catenates, due to a Cu-1,10-phenanthroline ( phen) ([Cu( phen) 2 ] + ) core, in which two rings become linked as a result of tetrahedral complexation of two phens to Cu(I). Thus, a fixed distance between electron donor and electron acceptor is achieved, yielding relatively long lived charge separated states (CSS) upon irradiation.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C₆₀as the acceptor

et al. 2015

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A new series of nanoscale electron donor-acceptor systems with [2]catenane architectures has been synthesized, incorporating magnesium porphyrin (MgP) or free base porphyrin (H 2 P) as electron donor and C 60 as electron acceptor, surrounding a central tetrahedral Cu(I)-1,10-phenanthroline ( phen) complex.Model catenated compounds incorporating only one or none of these photoactive moieties were also prepared. The synthesis involved the use of Sauvage's metal template protocol in combination with the 1,3-dipolar cycloaddition of azides and alkynes ("click chemistry"), as in other recent reports from our laboratories. Ground state electron interactions between the individual constituents was probed using electrochemistry and UV-vis absorption spectroscopy, while events occurring following photoexcitation in tetrahydrofuran (under both aerobic and anaerobic conditions) at various wavelengths were followed by means of time-resolved transient absorption and emission spectroscopies on the femtosecond and nanosecond time scales, respectively, complemented by measurements of quantum yields for generation of singlet oxygen. From similar studies with model catenates containing one or neither of the chromophores, the events following photoexcitation could be elucidated. The results were compared with those previously reported for analogous catenates based on zinc porphyrin (ZnP). It was determined that a series of energy transfer (EnT) and electron transfer (ET) processes take place in the present catenates, ultimately generating long-distance charge separated (CS) states involving oxidized porphyrin and reduced C 60 moieties, with lifetimes ranging from 400 to 1060 nanoseconds. Shorter lived short-distance CS states possessing oxidized copper complexes and reduced C 60 , with lifetimes ranging from 15 to 60 ns, were formed en route to the long-distance CS states. The dynamics of the ET processes were analyzed in terms of their thermodynamic driving forces. It was clear that intramolecular back ET was occurring in the inverted region of the Marcus parabola correlating rates and driving forces for electron transfer processes. In addition, evidence for triplet excited states as a product of either incomplete ET or back ET was found. The differences in behavior of the three catenates upon photoexcitation are analyzed in terms of the energy levels of the various intermediate states and the driving forces for EnT and ET processes.

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Section: Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C₆₀as the acceptor

et al. 2015

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“…2,9-di(4-anisyl)-1,10-phenanthroline was synthesized using the method reported by Gilman et al [12] with modifications. In a 50 mL round bottom flask equipped with a magnetic stirrer, a condenser and an argon inlet were placed 20 mL of dry ether and freshly cut lithium peaces (0.5g, 0.072 mol) at room temperature.…”

Section: Synthesis Of 29-di(4-anisyl)-110-phenanthrolinementioning

confidence: 99%

Synthesis and characterization of new phenanthrolinetriether copolymers with rotaxane architecture

Farcas¹,

Harabagiu²

2006

E-Polymers

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This paper is devoted to the preparation and characterization of new phenanthroline-triether copolymers with rotaxane architecture by reaction of complexes of α-or β-cyclodextrin and tri(ethylene glycol) ditosylate with 2,9-di(4-hydroxyphenyl)-1,10-phenanthroline, which is large enough to prevent dethreading of cyclodextrin molecules. Comparative 1 H-NMR analysis of tri(ethylene glycol) ditosylate complexes and of rotaxane copolymers evidenced the lower cyclodextrin content in rotaxane copolymers as compared to the calculated values. The rotaxane copolymers present bimodal molecular weight distributions attributed to the separation of the fractions with different content of cyclodextrin threaded on the copolymer chain. As evidenced by thermogravimetric analysis, the rotaxane copolymers show higher thermal stability than its non-complexed homologue.

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“…It can thus be considered as the "universal precursor" of dpp-based copper catenanes [15]. The archetype of the family of copper [2]catenanes, Cu(1) + was thus synthesized using Cu(I) as a 3D template and 2,9-bis(p-hydroxyphenyl)-1,10-phenanthroline as ligand.…”

confidence: 99%

“…A macrocycle containing a 2,9-diaryl-1,10-phenanthroline (synthesized in several steps from commercially available compounds) [15] was covalently linked to a linear 2,9-dimethyl-3,8-bis-(p-hy- 4 ]PF 6 in CH 3 CN/CH 2 Cl 2 at room temperature led quantitatively to 4 2+ as its PF 6 -salt (Fig. 11).…”

Section: Molecular Machines Constructed On Transition Metal-containinmentioning

confidence: 99%

Rotaxanes and Catenanes as Prototypes of Molecular Machines and Motors

et al. 2004

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In the course of the last 20 years, our view on rotaxanes and catenanes has completely changed. Copper(I)-templated strategies, in particular, have allowed us to prepare catenanes on a real preparative scale, in a few chemical steps from commercially available compounds. A particularly significant improvement was the introduction of the recently developed ring-closing metathesis reaction, using Grubbs catalyst. The dynamic properties of rotaxanes and catenanes has been exploited to construct molecular systems for which one component can be set in motion under the action of an external signal, while the other components can be considered as motionless (artificial molecular "machines" and "motors"). A particularly representative example is that of a rotaxane dimer, whose overall length can be controlled chemically: A metal exchange reaction (Cu I /Zn II ) triggers a reversible contraction/stretching process of the same molecular assembly, in a way reminiscent of the functioning of biological muscles.

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Templated synthesis of interlocked macrocyclic ligands, the catenands. Preparation and characterization of the prototypical bis-30 membered ring system

Cited by 238 publications

References 26 publications

Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C₆₀as the acceptor

Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C₆₀as the acceptor

Synthesis and characterization of new phenanthrolinetriether copolymers with rotaxane architecture

Rotaxanes and Catenanes as Prototypes of Molecular Machines and Motors

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Templated synthesis of interlocked macrocyclic ligands, the catenands. Preparation and characterization of the prototypical bis-30 membered ring system

Cited by 238 publications

References 26 publications

Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C60as the acceptor

Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C60as the acceptor

Synthesis and characterization of new phenanthrolinetriether copolymers with rotaxane architecture

Rotaxanes and Catenanes as Prototypes of Molecular Machines and Motors

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Product

Resources

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Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C₆₀as the acceptor

Synthesis and photophysical properties of new catenated electron donor–acceptor materials with magnesium and free base porphyrins as donors and C₆₀as the acceptor