A molecular Popeye: Li+@C60 and its complexes with [n]cycloparaphenylenes

Freiberger, Markus; Solymosi, Iris; Freiberger, Eva Marie; Hirsch, Andreas; Pérez‐Ojeda, M. Eugenia; Drewello, Thomas

doi:10.1039/d2nr07166e

Cited by 4 publications

(3 citation statements)

References 48 publications

(136 reference statements)

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“…Inspired by our recently reported trisbenzene complexes of heavy alkaline earth metals and host–guest properties of CPPs, − the heavy alkaline earth metals Ca, Sr, and Ba were tried as the guest atoms to be hosted at the center of [3]CPP. Delightfully, the [Ca©[3]CPP] complex was found to be a symmetric D 3 h energy minimum with the [3]CPP skeleton at the MN15/BS1 level (Figure a).…”

Section: Resultsmentioning

confidence: 99%

“…Herein, we propose that the [3]CPP skeleton as a host may be stabilized by a guest metal atom. We were inspired by the host–guest properties of CPPs − and the recently proposed trisbenzene complexes of alkaline-earth metals M(C 6 H 6 ) 3 (M = Ca, Sr, and Ba), where M atoms exhibited the transition-metal-like bonding behaviors of heavy alkaline-earth metals. − Note that the alkaline-earth metal-centered [3]CPP complexes [M©[3]CPP] can be seen as the product of dehydrogenated M(C 6 H 6 ) 3 complexes (Figure a).…”

Section: Introductionmentioning

confidence: 99%

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[Sc©[3]CPP]⁺: A Viable Metal-Centered [3]Cycloparaphenylene

Bian

Jin

et al. 2023

Inorg. Chem.

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[n]Cycloparaphenylenes ([n]CPPs, n denotes the number of phenyl groups) are difficult to synthesize because of the strain related to their bent phenyl rings. In particular, the strain in [3]CPP is high enough to destroy the π electron delocalization, leading to the spontaneous structural transition to an energetically more stable “bond-shift” (BS) isomer ([3]BS). In this contribution, we propose to achieve [3]CPP by enhancing the π electron delocalization through hosting a guest metal atom. Our computations revealed that Sc could stabilize [3]CPP by forming the [Sc©[3]CPP]+ complex through the favorable π-Sc donation–backdonation interactions. Thermodynamically, the binding energy between the Sc atom and [3]CPP was −205.7 kcal/mol, which could well compensate not only the energy difference of 44.2 kcal/mol between [3]CPP and [3]BS but also the extremely high strain energy of 170.3 kcal/mol in [3]CPP. Simultaneously, the [Sc©[3]CPP]+ complex is stable up to 1500 K in dynamic simulations, suggesting its high viability in the synthesis.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

[Sc©[3]CPP]⁺: A Viable Metal-Centered [3]Cycloparaphenylene

Bian

Jin

et al. 2023

Inorg. Chem.

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“…In a recent series of collision studies aimed at the establishment of host–guest bond strengths, we successfully transferred noncovalent CPP-based host–guest complexes from solution into the gas phase. − Here we present a detailed examination of the gas-phase stabilities of ([ n + x ]CPP⊃[ n ]CPP) +• ( n = 5–9; x = 3–7; n + x ≤ 12) (Table ) and ([11]CPP⊃[12]CNB) +• ring-in-ring complexes, based on the powerful combination of electrospray ionization (ESI) with tandem mass spectrometry (MS 2 ).…”

Section: Introductionmentioning

confidence: 99%

New Insights into Ring-In-Ring Complexes of [n]Cycloparaphenylenes including the [12]Carbon Nanobelt

Freiberger,

Frühwald,

Minameyer

et al. 2023

J. Phys. Chem. A

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The supramolecular chemistry of cycloparaphenylenes (CPPs) is characterized by the ability of the ring system to undergo both concave and convex π−π interactions. As a consequence, ring-in-ring complexes can be formed in which the CPP serves as the host as well as the guest molecule ([n + x]CPP⊃[n]CPP). In this work, host−guest ring-in-ring complexes of [n]CPPs (n = 5−12) are investigated by means of electrospray ionization-tandem mass spectrometry (ESI-MS 2 ) and laser desorption ionization mass spectrometry (LDI-MS). Extending the experimentally known complexes with ring size differences of five and six phenyl units (x = 5 and 6), we observe complexes with ring size differences of three up to seven phenyl units (x = 3−7). Energy-resolved collision experiments reveal that the charge is mainly located at the inner ring and complexes with phenyl unit differences of five and six are the most stable. In complexes featuring the same size difference, the complex stabilities slightly increase with an increasing size of the involved [n]CPPs. Utilizing the π-extended [12]carbon nanobelt ([12]CNB) as the guest also revealed an increase in complex stability. This study paves the way for a deeper understanding of the host−guest chemistry of CPPs.

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Sugar‐Bridged Fullerene Dumbbells and Their Interaction with the [10]Cycloparaphenylene Nanoring

Jakšić

Solymosi

Hirsch

et al. 2023

Chemistry A European J

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The synthesis and characterization of four dumbbell‐shaped fullerene molecules connected by isosorbide and isomannide moieties is presented. Additionally, their electrochemical behavior and their ability to form complexes with [10]cycloparaphenylene ([10]CPP) were investigated. The cyclic voltammetry (CV) results of the fullerene dumbbells demonstrate a high electron affinity, indicating their strong interaction with electron‐donating counterparts such as carbon nanorings, which possess complementary charge and shape properties. To study the thermodynamic and kinetic parameters of complexation, isothermal titration calorimetry (ITC) was employed. NMR titration experiments provided further insights into the binding stoichiometries. Two distinct approaches were utilized to create bridged structures: one based on cyclopropane and the other based on furan. Regardless of the type of linker used, all derivatives formed conventional 2 : 1 complexes denoted as [10]CPP2⊃C60derivative. However, the methano‐dumbbell molecules exhibited distinct binding behavior, resulting in the formation of mono‐ and bis‐pseudorotaxanes, as well as oligomers (polymers). The formation of linear polymers holds significant potential for applications in solar energy conversion processes.

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A molecular Popeye: Li⁺@C₆₀ and its complexes with [n]cycloparaphenylenes

Abstract: In this work, we compare for the first time the stability of [n]cycloparaphenylene ([n]CPP)-based host-guest complexes with Li+@C60 and C60 in the gas and the solution phase. Our gas-phase experiments...

Cited by 4 publications

References 48 publications

[Sc©[3]CPP]⁺: A Viable Metal-Centered [3]Cycloparaphenylene

[Sc©[3]CPP]⁺: A Viable Metal-Centered [3]Cycloparaphenylene

New Insights into Ring-In-Ring Complexes of [n]Cycloparaphenylenes including the [12]Carbon Nanobelt

Sugar‐Bridged Fullerene Dumbbells and Their Interaction with the [10]Cycloparaphenylene Nanoring

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A molecular Popeye: Li+@C60 and its complexes with [n]cycloparaphenylenes

Abstract: In this work, we compare for the first time the stability of [n]cycloparaphenylene ([n]CPP)-based host-guest complexes with Li+@C60 and C60 in the gas and the solution phase. Our gas-phase experiments...

Cited by 4 publications

References 48 publications

[Sc©[3]CPP]+: A Viable Metal-Centered [3]Cycloparaphenylene

[Sc©[3]CPP]+: A Viable Metal-Centered [3]Cycloparaphenylene

New Insights into Ring-In-Ring Complexes of [n]Cycloparaphenylenes including the [12]Carbon Nanobelt

Sugar‐Bridged Fullerene Dumbbells and Their Interaction with the [10]Cycloparaphenylene Nanoring

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A molecular Popeye: Li⁺@C₆₀ and its complexes with [n]cycloparaphenylenes

[Sc©[3]CPP]⁺: A Viable Metal-Centered [3]Cycloparaphenylene

[Sc©[3]CPP]⁺: A Viable Metal-Centered [3]Cycloparaphenylene