scholarly journals Bathophenanthroline Disulfonate Ligand-Induced Self-Assembly of Ir(III) Complexes in Water: An Intriguing Class of Photoluminescent Soft Materials

ACS Omega ◽  
2018 ◽  
Vol 3 (10) ◽  
pp. 14027-14038
Author(s):  
Michelle M. McGoorty ◽  
Abhishek Singh ◽  
Thomas A. Deaton ◽  
Benjamin Peterson ◽  
Chelsea M. Taliaferro ◽  
...  
Keyword(s):  
Self Assembly ◽  
Soft Materials ◽  
Bathophenanthroline Disulfonate

scholarly journals Chirality, Gelation Ability and Crystal Structure: Together or Apart? Alkyl Phenyl Ethers of Glycerol as Simple LMWGs

Symmetry ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 732
Author(s):  
Alexander A. Bredikhin ◽  
Aidar T. Gubaidullin ◽  
Zemfira A. Bredikhina ◽  
Robert R. Fayzullin ◽  
Olga A. Lodochnikova
Keyword(s):  
Self Assembly ◽  
Chiral Recognition ◽  
Soft Materials ◽  
Gelling Agent ◽  
Low Molecular Weight ◽  
X Ray Diffraction ◽  
X Ray ◽  
Different Types ◽  
Low Molecular Weight Gelators ◽  
Phenyl Ethers

Chiral recognition plays an important role in the self-assembly of soft materials, in particular supramolecular organogels formed by low molecular weight gelators (LMWGs). Out of 14 pairs of the studied racemic and enantiopure samples of alkyl-substituted phenyl ethers of glycerol, only eight enantiopure diols form the stable gels in nonane. The formation of gels from solutions was studied by polarimetry, and their degradation with the formation of xerogels was studied by the PXRD method. The revealed crystalline characteristics of all studied xerogels corresponded to those for crystalline samples of the parent gelators. In addition to those previously investigated, crystalline samples of enantiopure para-n-alkylphenyl glycerol ethers [alkyl = pentyl (5), hexyl (6), heptyl (7), octyl (8), nonyl (9)] and racemic 3-(3,5-dimethylphenoxy)propane-1,2-diol (rac-14) have been examined by single crystal X-ray diffraction analysis. Among 22 samples of compounds 1-14 studied by SC-XRD, seven different types of supramolecular motifs are identified, of which only two are realized in crystals of supramolecular gelators. An attempt was made to relate the ability to gel formation with the characteristics of the supramolecular motif of a potential gelling agent, and the frequency of formation of the motif, required for gelation, with the chiral characteristics of the sample.

scholarly journals Thermodynamics of structured fluids. Hard science for soft materials

2000 ◽  
Vol 72 (10) ◽  
pp. 1819-1834 ◽  
Author(s):  
John M. Prausnitz
Keyword(s):  
Self Assembly ◽  
Theoretical Calculations ◽  
Soft Materials ◽  
Confined Space ◽  
Molecular Physics ◽  
Fluid Structure ◽  
Light Emitting ◽  
Structured Fluids ◽  
Recent Developments ◽  
Narrow Space

At liquid-like densities, molecules of complex fluids can assume a variety of structures (or positions) in space; when the molecules contain many atoms as, for example, in polymers, that variety becomes very large. Further, when confined to a narrow space, it is possible to achieve structures that are not normally observed. Thanks to recent advances in statistical mechanics and molecular physics, and thanks to increasingly fast computers, it is now possible to calculate a fluid's structure, that is, the positions of molecules at equilibrium under given conditions. Calculation of fluid structure is useful because thermodynamic properties depend strongly on that structure, leading to possible applications for new materials. Three examples illustrate some recent developments; each example is presented only schematically (with a minimum of equations) to indicate the physical basis of the mathematical description. The first example considers the effect of branching on self-assembly (micellization) of copolymers (with possible long-range applications in medicine). The second and third examples consider the effect of confinement on fluid structure: first, crystallization in a narrow, confined space to produce a desired crystal structure (with possible applications for light-emitting diodes) and second, suppression of micellization of a diblock copolymer in a thin film (with possible application in lithography). Whenever possible, theoretical calculations are compared with experimental results.

scholarly journals Self-Assembly and Soft Material Preparation of Binary Organogels via Aminobenzimidazole/Benzothiazole and Acids with Different Alkyl Substituent Chains

2013 ◽  
Vol 2013 ◽  
pp. 1-11 ◽  
Author(s):  
Tifeng Jiao ◽  
Keren Ma ◽  
Xihai Shen ◽  
Qingrui Zhang ◽  
Xiujin Li ◽  
...  
Keyword(s):  
Organic Solvents ◽  
Self Assembly ◽  
Alkyl Substituent ◽  
Soft Materials ◽  
Spectral Studies ◽  
Hydrophobic Force ◽  
Benzothiazole Derivatives ◽  
Morphological Studies ◽  
Gelation Behavior ◽  
Potential Applications

The gelation behaviors of binary organogels composed of aminobenzimidazole/benzothiazole derivatives and benzoic acid with single-/multialkyl substituent chain in various organic solvents were designed and investigated. Their gelation behaviors in 20 solvents were tested as new binary organic gelators. This showed that the number and length of alkyl substituent chains and benzimidazole/benzothiazole segment have played a crucial role in the gelation behavior of all gelator mixtures in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. The length of alkyl substituent chains has also played an important role in changing the gelation behaviors and assembly states. Morphological studies revealed that the gelator molecules self-assemble into different aggregates from wrinkle, lamella, belt, to fiber with change of solvents. Spectral studies indicated that there existed different H-bond formation and hydrophobic force, depending on benzimidazole/benzothiazole segment and alkyl substituent chains in molecular skeletons. The prepared nanostructured materials have wide perspectives and many potential applications in nanoscience and material fields due to their scientific values. The present work may also give new clues for designing new binary organogelators and soft materials.

scholarly journals Preparation and Characterization of Binary Organogels via Some Azobenzene Amino Derivatives and Different Fatty Acids: Self-Assembly and Nanostructures

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
Haiying Guo ◽  
Tifeng Jiao ◽  
Xihai Shen ◽  
Qingrui Zhang ◽  
Adan Li ◽  
...  
Keyword(s):  
Fatty Acids ◽  
Organic Solvents ◽  
Self Assembly ◽  
Alkyl Substituent ◽  
Soft Materials ◽  
Spectral Studies ◽  
Hydrophobic Force ◽  
Alkyl Chains ◽  
Morphological Studies ◽  
Amino Derivatives

In present work the gelation behaviors of binary organogels composed of azobenzene amino derivatives and fatty acids with different alkyl chains in various organic solvents were designed and investigated. Their gelation behaviors in 20 solvents were tested as new binary organic gelators. It showed that the length of alkyl substituent chains and azobenzene segment have played a crucial role in the gelation behavior of all gelator mixtures in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Morphological studies revealed that the gelator molecules self-assemble into different aggregates from lamella, wrinkle, to belt with change of solvents. Spectral studies indicated that there existed different H-bond formation and hydrophobic force, depending on different substituent chains in molecular skeletons. The present work may also give new perspectives for designing new binary organogelators and soft materials.

Soft materials with graphitic nanostructures

2007 ◽  
Vol 365 (1855) ◽  
pp. 1539-1552 ◽  
Author(s):  
Takuzo Aida ◽  
Takanori Fukushima
Keyword(s):  
Carbon Nanotubes ◽  
Ionic Liquids ◽  
Self Assembly ◽  
Soft Materials ◽  
Review Article ◽  
New Family ◽  
Nanotube Composites ◽  
Long Time ◽  
Walled Carbon Nanotubes ◽  
Imidazolium Ion

This review article focuses on our recent studies on novel soft materials consisting of carbon nanotubes. Single-walled carbon nanotubes, when suspended in imidazolium ion-based ionic liquids and ground in an agate mortar, form physical gels (bucky gels), where heavily entangled bundles of carbon nanotubes are exfoliated to give highly dispersed, much finer bundles. By using bucky gels, the first printable actuators that operate in air for a long time without any external electrolyte are developed. Furthermore, the use of polymerizable ionic liquids as the gelling media results in the formation of electroconductive polymer/nanotube composites with enhanced mechanical properties. The article also highlights a new family of nanotubular graphite, via self-assembly of amphiphilic hexabenzocoronene (HBC) derivatives. The nanotubes consist of a graphitic wall composed of a great number of π-stacked HBC units and are electroconductive upon oxidation. The use of amphiphilic HBCs with functional groups results in the formation of nanotubes with various interesting properties.

scholarly journals Porous Colloidal Hydrogels Formed by Coordination-Driven Self-Assembly of Charged Metal-Organic Polyhedra

2021 ◽  
Author(s):  
Zaoming Wang ◽  
Gavin Craig ◽  
alexandre legrand ◽  
Frederik Haase ◽  
Saori Minami ◽  
...  
Keyword(s):  
Self Assembly ◽  
Soft Materials ◽  
Building Blocks ◽  
Internal Cavity ◽  
Hydroxyl Groups ◽  
Gel Formation ◽  
Gas Sorption ◽  
Coordination Cages ◽  
Metal Organic ◽  
Supramolecular Polymerization

Introduction of porosity into supramolecular gels endows soft materials with functionalities for molecular encapsulation, release, separation and conversion. Metal-organic polyhedra (MOPs), discrete coordination cages containing an internal cavity, have recently been employed as building blocks to construct polymeric gel networks with potential porosity. However, most of the materials can only be synthesized in organic solvents, and the examples of porous, MOP-based hydrogels are scarce. Here, we demonstrate the fabrication of porous hydrogels based on [Rh<sub>2</sub>(OH-bdc)<sub>2</sub>]<sub>12</sub>, a rhodium-based MOP containing hydroxyl groups on its periphery (OH-bdc = 5-hydroxy-1,3-benzenedicarboxylate). By simply deprotonating [Rh<sub>2</sub>(OH-bdc)<sub>2</sub>]<sub>12</sub> with the base NaOH, the supramolecular polymerization between MOPs and organic linkers can be induced in the aqueous solution, leading to the kinetically controllable formation of hydrogels with hierarchical colloidal networks. When heating the deprotonated MOP, Na<sub>x</sub>[Rh<sub>24</sub>(O-bdc)<sub>x</sub>(OH-bdc)<sub>24-x</sub>], to induce gelation, the MOP was found to partially decompose, affecting the mechanical property of the resulting gels. By applying a post-synthetic deprotonation strategy, we show that the deprotonation degree of the MOP can be altered after the gel formation without serious decomposition of the MOPs. Gas sorption measurements confirmed the permanent porosity of the corresponding aerogels obtained from these MOP-based hydrogels, showing potentials for applications in gas sorption and catalysis.

Spatiotemporal Control of Supramolecular Polymerization and Gelation of Metal-Organic Polyhedra

2020 ◽  
Author(s):  
alexandre legrand ◽  
Li-Hao Liu ◽  
Philipp Royla ◽  
Takuma Aoyama ◽  
Gavin Craig ◽  
...  
Keyword(s):  
Acid Concentration ◽  
Self Assembly ◽  
Colloidal Particles ◽  
Soft Materials ◽  
Supramolecular Materials ◽  
Time Resolved ◽  
Colloidal Gel ◽  
Metal Organic ◽  
Spatiotemporal Control ◽  
Gel Network

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA), and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption and <sup>1</sup>H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

Irᴵᴵᴵ as a Strategy for Preorganization in H-Bonded Motifs

2019 ◽  
Author(s):  
Barbora Balonova ◽  
Helena J. Shepherd ◽  
Christopher Serpell ◽  
Barry Blight
Keyword(s):  
Hydrogen Bonding ◽  
Metal Complexes ◽  
General Formula ◽  
Self Assembly ◽  
Structural Design ◽  
Functional Materials ◽  
Soft Materials ◽  
Thiourea Derivatives ◽  
Hydrogen Bonded Systems ◽  
Hydrogen Bonded

Here we present the synthesis and characterisation of four hydrogen bonded systems based on thiourea derivatives. These motifs are considered to be stable and desirable for supramolecular hydrogen-bonded functional materials. Interpretation of the structural design of thiourea based ligand and its incorporation into metal complexes can contribute to the understanding of preorganised self-assembly and open new pathways in design of novel soft materials. This work contributes to the unexplored library of hydrogen bonded metal complexes based on iridium. Further we examined the photoluminescence of the system of general formula [Ir(C^N)<sub>2</sub>(N^S)] and the effect of hydrogen bonding on the emission properties when combined with different <i>n</i>-heteroacenes.

scholarly journals Nanostructures and Self-Assembly of Organogels via Benzimidazole/Benzothiazole Imide Derivatives with Different Alkyl Substituent Chains

2013 ◽  
Vol 2013 ◽  
pp. 1-8 ◽  
Author(s):  
Xihai Shen ◽  
Tifeng Jiao ◽  
Qingrui Zhang ◽  
Haiying Guo ◽  
Yaopeng Lv ◽  
...  
Keyword(s):  
Organic Solvents ◽  
Self Assembly ◽  
Bond Formation ◽  
Alkyl Substituent ◽  
Soft Materials ◽  
Molecular Structures ◽  
Spectral Studies ◽  
Hydrophobic Force ◽  
Alkyl Chains ◽  
Gelation Behavior

New benzimidazole/benzothiazole imide derivatives with different alkyl substituent chains were designed and synthesized. Their gelation behaviors in 22 solvents were tested as novel low-molecular-mass organic gelators. The test showed that the alkyl substituent chains and headgroups of benzimidazole/benzothiazole residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. SEM and AFM observations revealed that the gelator molecules self-assemble into different aggregates from wrinkle, lamella and belt to dot with change of solvents. Spectral studies indicated that there existed different H-bond formation between imide groups and hydrophobic force of alkyl substituent chains in molecular skeletons. The present work may give some insights into design and character of new organogelators and soft materials with special molecular structures.

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