Self-Assembly of a Chiral Cubic Three-Connected Net from the High Symmetry Molecules C60 and SnI4

Author(s):  
Daniel B. Straus ◽  
Robert J. Cava

The design of new chiral materials usually requires stereoselective organic synthesis to create molecules with chiral centers. Less commonly, achiral molecules can self-assemble into chiral materials, despite the absence of intrinsic molecular chirality. Here, we demonstrate the assembly of high-symmetry molecules into a chiral van der Waals structure by synthesizing crystals of C<sub>60</sub>(SnI<sub>4</sub>)<sub>2</sub> from icosahedral buckminsterfullerene (C<sub>60</sub>) and tetrahedral SnI4 molecules through spontaneous self-assembly. The SnI<sub>4</sub> tetrahedra template the Sn atoms into a chiral cubic three-connected net of the SrSi<sub>2</sub> type that is held together by van der Waals forces. Our results represent the remarkable emergence of a self-assembled chiral material from two of the most highly symmetric molecules, demonstrating that almost any molecular, nanocrystalline, or engineered precursor can be considered when designing chiral assemblies.

2020 ◽  
Author(s):  
Daniel B. Straus ◽  
Robert J. Cava

The design of new chiral materials usually requires stereoselective organic synthesis to create molecules with chiral centers. Less commonly, achiral molecules can self-assemble into chiral materials, despite the absence of intrinsic molecular chirality. Here, we demonstrate the assembly of high-symmetry molecules into a chiral van der Waals structure by synthesizing crystals of C<sub>60</sub>(SnI<sub>4</sub>)<sub>2</sub> from icosahedral buckminsterfullerene (C<sub>60</sub>) and tetrahedral SnI4 molecules through spontaneous self-assembly. The SnI<sub>4</sub> tetrahedra template the Sn atoms into a chiral cubic three-connected net of the SrSi<sub>2</sub> type that is held together by van der Waals forces. Our results represent the remarkable emergence of a self-assembled chiral material from two of the most highly symmetric molecules, demonstrating that almost any molecular, nanocrystalline, or engineered precursor can be considered when designing chiral assemblies.


2020 ◽  
Author(s):  
Daniel B. Straus ◽  
Robert J. Cava

The design of new chiral materials usually requires stereoselective organic synthesis to create molecules with chiral centers. Less commonly, achiral molecules can self-assemble into chiral materials, despite the absence of intrinsic molecular chirality. Here, we demonstrate the assembly of high-symmetry molecules into a chiral van der Waals structure by synthesizing crystals of C<sub>60</sub>(SnI<sub>4</sub>)<sub>2</sub> from icosahedral buckminsterfullerene (C<sub>60</sub>) and tetrahedral SnI<sub>4</sub> molecules through spontaneous self-assembly. Our results represent the remarkable emergence of chirality from the self-assembly of two of the most highly symmetric molecules, demonstrating that almost any molecular precursor can be considered when designing chiral assemblies.


RSC Advances ◽  
2019 ◽  
Vol 9 (8) ◽  
pp. 4530-4538 ◽  
Author(s):  
Siyu He ◽  
Nan Zhang ◽  
Pu Jing

Stability of chlorophylls was improved with self-assembly of chlorophylls and NaCas nanoparticles via van der Waals forces and hydrogen bonds.


2021 ◽  
Author(s):  
Daniel B. Straus ◽  
Robert J. Cava

We describe the spontaneous chiral self-assembly of C<sub>70</sub> with SnI<sub>4</sub> as well as a mixture of C<sub>60</sub> and C<sub>70</sub> with SnI<sub>4</sub>. Macroscopic single crystals with the formula (C<sub>70</sub>)<sub>x</sub>(C<sub>60</sub>)<sub>1-x</sub>(SnI<sub>4</sub>)<sub>2</sub> (x = 0-1) are reported. C<sub>60</sub>, which is spherical, and C<sub>70</sub>, which is ellipsoidal, form a solid solution in these crystals, and the cubic lattice parameter of the chiral phase linearly increases as x grows from 0 to 1 in accordance with Vegard’s law. Our results demonstrate that nonspherical particles and polydispersity are not an impediment to the growth of chiral crystals from high-symmetry achiral precursors, providing a route to assemble achiral particles including colloidal nanocrystals and engineered nanostructures into chiral materials without the need to use external templates.<br>


2009 ◽  
Vol 79-82 ◽  
pp. 341-344 ◽  
Author(s):  
Li Na Chen ◽  
Yan Li Chen ◽  
Pei Hua Zhu ◽  
Guo Xin Sun ◽  
Hong Yan Wang ◽  
...  

phthalocyanine, porphyrin, sandwich rare earth complex, nanostructure, self-assembly. Abstract. Three novel sandwich-type mixed (phthalocyaninato)(porphyrinato) rear earth complexes, namely Ce(DPP)(Pc)(1), Sm2(DPP)(Pc)2(2) and Sm2(DPP)2(Pc)(3) [Pc = dianion of phthalocyanine, DPP= dianion of 5,15-di(phenyl)porphyrin], have been fabricated into nano-assemblies onto the SiO2 surface by a surface assisted solvent-vapor annealing method. The effect of the number of porphyrin and phthalocyanine ligands on the morphology of self-assembled nanostructures of these double- and triple-decker complexes has been systematically studied. Competition and cooperation between the inter-molecular - interaction, van der Waals, and metal-ligand coordination for different compounds results in nanostructures with different morphology from approximately spherical shape with average size of ~300 nm and ~400 nm for 1 and 2, respectively, nano-rods with aspect ratio (length over width) around 5 for 3, which were characterized by electronic absorption, X-ray diffraction (XRD), and atomic force microscopy (AFM). Electronic absorption spectroscopic results reveal the formation of J-aggregates in the nano-structures and suggest the increasing - interaction in the order of 3, 1, to 2. Examination by XRD reveal that in the nanostructures of compounds 1-3, a dimeric supramolecular structure was formed through an intermolecular - interaction and/or van der Waals between two sandwich-type molecules, which as the building block self-assembles into the target nanostructures.


2021 ◽  
Author(s):  
Daniel B. Straus ◽  
Robert J. Cava

We describe the spontaneous chiral self-assembly of C<sub>70</sub> with SnI<sub>4</sub> as well as a mixture of C<sub>60</sub> and C<sub>70</sub> with SnI<sub>4</sub>. Macroscopic single crystals with the formula (C<sub>70</sub>)<sub>x</sub>(C<sub>60</sub>)<sub>1-x</sub>(SnI<sub>4</sub>)<sub>2</sub> (x = 0-1) are reported. C<sub>60</sub>, which is spherical, and C<sub>70</sub>, which is ellipsoidal, form a solid solution in these crystals, and the cubic lattice parameter of the chiral phase linearly increases as x grows from 0 to 1 in accordance with Vegard’s law. Our results demonstrate that nonspherical particles and polydispersity are not an impediment to the growth of chiral crystals from high-symmetry achiral precursors, providing a route to assemble achiral particles including colloidal nanocrystals and engineered nanostructures into chiral materials without the need to use external templates.<br>


CrystEngComm ◽  
2019 ◽  
Vol 21 (4) ◽  
pp. 602-615 ◽  
Author(s):  
Mohadeseh A. Baboli ◽  
Michael A. Slocum ◽  
Hyun Kum ◽  
Thomas S. Wilhelm ◽  
Stephen J. Polly ◽  
...  

Self-assembly of InAs nanowire arrays with highest reported aspect ratios and number density by van der Waals epitaxy on graphene is presented.


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