Non‐Centrosymmetric Homochiral Supramolecular Polymers of Tetrahedral Subphthalocyanine Molecules

Guilleme, Julia; Muñoz, Marı́a A.; Calbo, Joaquín; Aragó, Juan; Viruela, Pedro M.; Ortı́, Enrique; Torres, Tomás; González‐Rodríguez, David

doi:10.1002/anie.201411272

“…[3-5, 9b,13a] Thes tacking interaction between the b-diketonate and the NIT phenyl ring may be the driving force for the creation of these screw chains. TbNIT-Ph-O-Hexyl also recalls similar structures with alkyl chains such as homochiral supramolecular subphthalocyanine columns, [18] a-cyclodextrin organic nanotubes, [19] or Cu I supramolecular helixes. [20] Additionally,t he chiral nature of the nanotubes makes TbNIT-Ph-O-Hexyl agood candidate to observe electric field modulation of magnetic exchange [21] or magneto-chiral dichroism [9b] as observed on NIT-based chains with 3d metal ions.C hiral Ln-NIT chain appears very appealing for the coexistence of strong spin-orbit coupling and frustrated magnetic interactions.…”

Section: Angewandte Chemiementioning

confidence: 97%

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Houard

¹

,

Evrard

²

,

Calvez

³

et al. 2019

View full text Add to dashboard Cite

We report a single‐chain magnet (SCM) made of a terbium(III) building block and a nitronyl‐nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long‐range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self‐organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each TbIII ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite‐size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc=2400 Oe MR=2.09 μB at 0.5 K) for this class of compounds.

show abstract

“…The stacking interaction between the β‐diketonate and the NIT phenyl ring may be the driving force for the creation of these screw chains. TbNIT‐Ph‐O‐Hexyl also recalls similar structures with alkyl chains such as homochiral supramolecular subphthalocyanine columns, α‐cyclodextrin organic nanotubes, or Cu I supramolecular helixes …”

Section: Figurementioning

confidence: 93%

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Houard

¹

,

Evrard

²

,

Calvez

³

et al. 2019

View full text Add to dashboard Cite

We report a single‐chain magnet (SCM) made of a terbium(III) building block and a nitronyl‐nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long‐range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self‐organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each TbIII ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite‐size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc=2400 Oe MR=2.09 μB at 0.5 K) for this class of compounds.

show abstract

“…Recognizing the need to drive solid-state organization in these electrically active materials, recent reports have detailed peripheral substitution of the SubPc core to induce self assembly in both solution and the solid state. [25][26][27][28] These reports, however, are limited to structural studies of these compounds; their charge-and energy transfer characteristics were not elucidated.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Axially Functionalized Subphthalocyanines in Thin Films

Ren

¹

,

Hiszpanski

²

,

Loo

³

2015

View full text Add to dashboard Cite

The addition of trialkoxylbenzyloxyl substituents at the axial position of conformationally non-planar SubPc promotes its solid-state self assembly. Unlike prior SubPc derivatives, photophysical studies suggest the presence of intermolecular electronic coupling between neighboring cores of SubPc derivatives, the strength of which depends on both the electronic nature of the core -which we tune through fluorination -and the extent of van der Waals interactions originating from the alkyl side chains on the trialkoxylbenzyloxyl tail. Modulating the relative strength of core-core and van der Waals interactions introduces morphological richness and provides access to liquid-crystalline hexagonal and smectic phases. When core-core interactions are strong, thin films of SubPc spontaneously adopt a highly crystalline lamellar structure in the solid state. Thin films of trialkoxylbenzyloxylsubstituted SubPcs thus support efficient energy and charge transfer given their intermolecular electronic communication and longrange order. INTRODUCTION:Guiding self-organization of organic π-conjugated molecules is essential to facilitate efficient charge and energy transfer in organic electronics. 1-6 To promote long range order, intermolecular interactions, such as ionic interactions, hydrogenbonding, π-π interactions, and van der Waals interactions, must work cooperatively to induce the spontaneous formation of hierarchical structures from basic molecular units. 7,8,9 Among organic π-conjugated molecules, conformationally non-planar systems are getting increasing attention in organic electronics. 10-13 Having a bowl-shaped conformation, subpthalocyanine (SubPc) is a special member of organic π-conjugated family. Derivatives of SubPc exhibit excellent photophysical properties, such as high absorptivity, high fluorescent quantum yield, and efficient charge/energy transfer, all of which have been exploited in areas of toxic anion sensing, two photo-absorption, and artificial photosynthetic systems. 14 SubPcs have also been successfully incorporated in high performance organic electronics, such as OLEDs, OFETs, and OPVs. 15-24 While SubPc crystals can form under stringent growth conditions, SubPc derivatives generally do not form ordered thin films, presumably because of the the non-planar conformation of the core. Given that charge transport in molecular semiconductors occurs via hopping, this lack of longrange order in SubPcs thin films is thought to limit the performance of devices that incorporate them. Recognizing the need to drive solid-state organization in these electrically active materials, recent reports have detailed peripheral substitution of the SubPc core to induce self assembly in both solution and the solid state. 25-28 These reports, however, are limited to structural studies of these compounds; their charge-and energy transfer characteristics were not elucidated.Different from previous reports, we have opted to axially functionalize SubPc with trialkoxylbenzyloxyl tails to drive assembly. As opposed to the phenoxyl ...

show abstract

Non‐Centrosymmetric Homochiral Supramolecular Polymers of Tetrahedral Subphthalocyanine Molecules

Abstract: Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in:

Cited by 72 publications

References 43 publications

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

Self-Assembly of Axially Functionalized Subphthalocyanines in Thin Films

Contact Info

Product

Resources

About