Highly strained [6]cycloparaphenylene: crystallization of an unsolvated polymorph and the first mono- and dianions

Spisak, Sarah N.; Wei, Zheng; Darzi, Evan R.; Jasti, Ramesh; Petrukhina, Marina A.

doi:10.1039/c8cc03693d

Cited by 57 publications

(64 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…An exception is the [6]CPP case, for which three different polymorphs have been found up to date. [19] These findings clearly reveal the subtle yet dominant effect of the weak intermolecular interactions driving the supra molecular self-assembly of these systems. [18] More recently, another polymorph of [6]CPP has been found when the crystallization is carried out by sublimation at 220 °C.…”

mentioning

confidence: 89%

“…[18] More recently, another polymorph of [6]CPP has been found when the crystallization is carried out by sublimation at 220 °C. [19] These findings clearly reveal the subtle yet dominant effect of the weak intermolecular interactions driving the supra molecular self-assembly of these systems. [19] These findings clearly reveal the subtle yet dominant effect of the weak intermolecular interactions driving the supra molecular self-assembly of these systems.…”

mentioning

confidence: 89%

“…In the case of the hexagonal structure, see Figure 3a, a simulation box containing 64 molecules were created from a rectangular unit cell with dimensions a = 14.203 Å and b = 24.599 Å replicated 8 × 4 over a rectangular graphite surface of dimensions A = 113.62 Å and B = 98.394 Å (temperature of 300 K during 10 ns). [19] for [6]CPP crystals growth by sublimation and deposition. For this reason, in order to optimize the packing of an adlayer composed by molecules in the vertical configuration, and starting from the HB structure mentioned before, we applied an external pressure of 1 atm to the system in the plane direction.…”

Section: Full-coveragementioning

confidence: 99%

See 2 more Smart Citations

Structure and Charge Transport Properties of Cycloparaphenylene Monolayers on Graphite

Pérez-Guardiola

Pérez-Jiménez

Muccioli³

et al. 2019

Adv Materials Inter

View full text Add to dashboard Cite

The synthesis of CPPs has been experimentally challenging due to the strain energy needed to close the ring. [7] Vögtle and co-workers [8,9] attempted to synthesize CPPs from macrocycles formed by arene and cyclohexane units to therefore reduce the strain energy of the system. However, the first synthesis of CPPs was afforded only by Jasti et al. [10] in 2008, followed by the first selective synthesis of CPPs by Itami and co-workers [11,12] using a modular approach to build [n]CPPs with n ⩾ 12. Other successfully strategies (Yamago et al. [13] ) use a square-shaped tetra platinum biphenyl complex as an intermediate to selectively synthesize the [8]CPP molecule. In the above mentioned works, it was possible to obtain CPPs in the milligram-scale, with Jasti and co-workers [6,14] producing the first gram-scale synthesis. The smallest CPP synthesized up to date is [5]CPP, [15] which shows the great success achieved so far in overcoming the strain energy.Concerning the supramolecular packing, the solid-state (3D) structure of CPPs has been characterized in several works by means of X-ray diffraction. [16,17] The molecules self-assemble in a herringbone (HB) pattern independently of their size, as it often happens for other π-conjugated systems. An exception is the [6]CPP case, for which three different polymorphs have been found up to date. The first solid-state characterization of [6]CPP revealed a tubular-like structure, [14] but a recent study revealed that the crystallographic structure might depend on the crystallization conditions, also finding a herringbone configuration a few kcal mol −1 more stable than the tubular one. [18] More recently, another polymorph of [6]CPP has been found when the crystallization is carried out by sublimation at 220 °C. In these conditions, no solvent molecules are occluded inside the [6]CPP cavity, and thus, a concave-convex structure appears (i.e., molecules tightly packed in a T-like shape minimizing the internal space inside the cavities). [19] These findings clearly reveal the subtle yet dominant effect of the weak intermolecular interactions driving the supra molecular self-assembly of these systems. Motivated by this, some of us investigated in a previous theoretical work the adsorption energies of [8]CPP on small carbon nanoflakes (circumcirmcumcoronene) and how these through-space weak forces can serve to immobilize the systems in energetically favored configuration. [20] In the present study, we wish to go a step further and employ a tailored force field and molecular dynamics (MD) simulations to predict the supramolecular structure of thin films of CPPs on graphite surfaces. The systematic exploration of the adsorption The nanoscale organization of cycloparaphenylene molecules when physisorbed on a graphite surface is theoretically investigated by means of atomistic molecular dynamics simulations employing a tailored and benchmarked force field. The landing of a single molecule is first considered, to progressively deposit more molecules to finally reach the full coverage...

show abstract

mentioning

confidence: 89%

mentioning

confidence: 89%

Section: Full-coveragementioning

confidence: 99%

See 1 more Smart Citation

Structure and Charge Transport Properties of Cycloparaphenylene Monolayers on Graphite

Pérez-Guardiola

Pérez-Jiménez

Muccioli³

et al. 2019

Adv Materials Inter

View full text Add to dashboard Cite

show abstract

“…The reaction product exhibited a strongly red‐shifted absorption band ( λ max =600 nm) and the solid‐state structure revealed ionic interactions between the K + ions and both the concave and convex π‐surfaces of [8]CPP . More recently, the same authors reported the one‐ and twofold reduction of [6]CPP , including evidence for the inclusion of THF in the cavity of the nanohoop …”

Section: Metal Coordinationmentioning

confidence: 99%

The Supramolecular Chemistry of Strained Carbon Nanohoops

2019

View full text Add to dashboard Cite

Since 1996, a growing number of strained macrocycles, comprising only sp2‐ or sp‐hybridized carbon atoms within the ring, have become synthetically accessible, with the [n]cycloparaphenyleneacetylenes (CPPAs) and the [n]cycloparaphenylenes (CPPs) being the most prominent examples. Now that robust and relatively general synthetic routes toward a diverse range of nanohoop structures have become available, the research focus is beginning to shift towards the exploration of their properties and applications. From a supramolecular chemistry perspective, these macrocycles offer unique opportunities as a result of their near‐perfect circular shape, the unusually high degree of shape‐persistence, and the presence of both convex and concave π‐faces. In this Minireview, we give an overview on the use of strained carbon‐rich nanohoops in host–guest chemistry, the preparation of mechanically interlocked architectures, and crystal engineering.

show abstract

“…Das Reaktionsprodukt wies eine stark rotverschobene Absorptionsbande auf ( λ max =600 nm), und die Festkörperstruktur zeigte ionische Wechselwirkungen von K + ‐Ionen sowohl mit der konkaven als auch mit der konvexen π‐Fläche von [8]CPP . Vor kurzem berichteten dieselben Autoren über die ein‐ und zweifache Reduktion von [6]CPP , einschließlich dem Beweis für die Einlagerung von THF in den Hohlraum des Nanoreifens …”

Section: Koordination An Metalleunclassified

Supramolekulare Chemie von gespannten Kohlenstoffnanoreifen

Delius

2019

Angewandte Chemie

View full text Add to dashboard Cite

Seit 1996 ist eine stetig wachsende Anzahl von hoch gespannten Makrozyklen präparativ zugänglich geworden, die lediglich sp2‐ oder sp‐hybridisierte Kohlenstoffatome im Ring enthalten, wobei [n]Cycloparaphenylenacetylene (CPPAs) und [n]Cycloparaphenylene (CPPs) die wichtigsten Beispiele dieser Klasse darstellen. Nachdem nun robuste und relativ allgemeine Synthesewege zu einer Vielzahl von Nanoreifen‐Strukturen zur Verfügung stehen, beginnt sich der Forschungsschwerpunkt auf die Erforschung ihrer Eigenschaften und Anwendungen zu verlagern. Aus Sicht der supramolekularen Chemie bieten diese Makrozyklen wegen ihrer nahezu perfekten Kreisform, der ungewöhnlich hohen Formstabilität und der Gegenwart von konvexen und konkaven π‐Flächen einzigartige Möglichkeiten. In diesem Kurzaufsatz besprechen wir den Einsatz von gespannten kohlenstoffreichen Nanoreifen in der Wirt‐Gast‐Chemie, der Herstellung von mechanisch verzahnten Architekturen und dem definierten Kristalldesign.

show abstract

Highly strained [6]cycloparaphenylene: crystallization of an unsolvated polymorph and the first mono- and dianions

Cited by 57 publications

References 46 publications

Structure and Charge Transport Properties of Cycloparaphenylene Monolayers on Graphite

Structure and Charge Transport Properties of Cycloparaphenylene Monolayers on Graphite

The Supramolecular Chemistry of Strained Carbon Nanohoops

Supramolekulare Chemie von gespannten Kohlenstoffnanoreifen

Contact Info

Product

Resources

About