Robust supramolecular nanocylinders of naphthalene diimide in water

The synthesis of conjugates of perylene diimide (PDI) and naphthalene diimide (NDI) modified with two benzo-21-crown-7 ethers (B21C7) are herein described. Their self-assembly behavior in various solvents was investigated particularly in aqueous medium, due to the recently discovered hydrophilic properties of B21C7 crown macrocycle. An unexpected fluorescence quenching phenomenon was observed in the PDI-B21C7 macrocycle conjugate in chloroform. The detailed UV–vis absorption and fluorescence spectra of these PDI/NDI derivatives in different solvents as well as their morphologies were investigated.

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Engineering Coordination and Supramolecular Copper−Organic Networks by Aqueous Medium Self-Assembly with 1,3,5-Triaza-7-phosphaadamantane (PTA)

Crystal Growth & Design ◽

10.1021/cg900334w ◽

2009 ◽

Vol 9 (7) ◽

pp. 3006-3010 ◽

Cited By ~ 45

Author(s):

Łukasz Jaremko ◽

Alexander M. Kirillov ◽

Piotr Smoleński ◽

Armando J. L. Pombeiro

Keyword(s):

Aqueous Medium ◽

Self Assembly ◽

Organic Networks

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Taming nitroformate through encapsulation with nitrogen-rich hydrogen-bonded organic frameworks

Nature Communications ◽

10.1038/s41467-021-22475-8 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Jichuan Zhang ◽

Yongan Feng ◽

Richard J. Staples ◽

Jiaheng Zhang ◽

Jean’ne M. Shreeve

Keyword(s):

Thermal Stability ◽

Hydrogen Bonds ◽

Self Assembly ◽

Energetic Materials ◽

Decomposition Temperature ◽

High Oxygen Content ◽

The Poor ◽

Simple Preparation ◽

First Time ◽

Hydrogen Bonded

AbstractOwing to its simple preparation and high oxygen content, nitroformate [−C(NO2)3, NF] is an extremely attractive oxidant component for propellants and explosives. However, the poor thermostability of NF-based derivatives has been an unconquerable barrier for more than 150 years, thus hindering its application. In this study, the first example of a nitrogen-rich hydrogen-bonded organic framework (HOF-NF) is designed and constructed through self-assembly in energetic materials, in which NF anions are trapped in pores of the resulting framework via the dual force of ionic and hydrogen bonds from the strengthened framework. These factors lead to the decomposition temperature of the resulting HOF-NF moiety being 200 °C, which exceeds the challenge of thermal stability over 180 °C for the first time among NF-based compounds. A large number of NF-based compounds with high stabilities and excellent properties can be designed and synthesized on the basis of this work.

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Acemetacin cocrystals and salts: structure solution from powder X-ray data and form selection of the piperazine salt

IUCrJ ◽

10.1107/s2052252514004229 ◽

2014 ◽

Vol 1 (2) ◽

pp. 136-150 ◽

Cited By ~ 37

Author(s):

Palash Sanphui ◽

Geetha Bolla ◽

Ashwini Nangia ◽

Vladimir Chernyshev

Keyword(s):

Hydrogen Bonds ◽

Dissolution Rate ◽

Aqueous Medium ◽

Acid Amide ◽

Three Dimensional ◽

X Ray Diffraction ◽

Reference Drug ◽

X Ray ◽

Time Period ◽

Solid Form

Acemetacin (ACM) is a non-steroidal anti-inflammatory drug (NSAID), which causes reduced gastric damage compared with indomethacin. However, acemetacin has a tendency to form a less soluble hydrate in the aqueous medium. We noted difficulties in the preparation of cocrystals and salts of acemetacin by mechanochemical methods, because this drug tends to form a hydrate during any kind of solution-based processing. With the objective to discover a solid form of acemetacin that is stable in the aqueous medium, binary adducts were prepared by the melt method to avoid hydration. The coformers/salt formers reported are pyridine carboxamides [nicotinamide (NAM), isonicotinamide (INA), and picolinamide (PAM)], caprolactam (CPR),p-aminobenzoic acid (PABA), and piperazine (PPZ). The structures of an ACM–INA cocrystal and a binary adduct ACM–PABA were solved using single-crystal X-ray diffraction. Other ACM cocrystals, ACM–PAM and ACM–CPR, and the piperazine salt ACM–PPZ were solved from high-resolution powder X-ray diffraction data. The ACM–INA cocrystal is sustained by the acid...pyridine heterosynthon and N—H...O catemer hydrogen bonds involving the amide group. The acid...amide heterosynthon is present in the ACM–PAM cocrystal, while ACM–CPR contains carboxamide dimers of caprolactam along with acid–carbonyl (ACM) hydrogen bonds. The cocrystals ACM–INA, ACM–PAM and ACM–CPR are three-dimensional isostructural. The carboxyl...carboxyl synthon in ACM–PABA posed difficulty in assigning the position of the H atom, which may indicate proton disorder. In terms of stability, the salts were found to be relatively stable in pH 7 buffer medium over 24 h, but the cocrystals dissociated to give ACM hydrate during the same time period. The ACM–PPZ salt and ACM–nicotinamide cocrystal dissolve five times faster than the stable hydrate form, whereas the ACM–PABA adduct has 2.5 times faster dissolution rate. The pharmaceutically acceptable piperazine salt of acemetacin exhibits superior stability, faster dissolution rate and is able to overcome the hydration tendency of the reference drug.

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Effects of Alkyl Chain Length and Hydrogen Bonds on the Cooperative Self-Assembly of 2-Thienyl-Type Diarylethenes at a Liquid/Highly Oriented Pyrolytic Graphite (HOPG) Interface

Chemistry - A European Journal ◽

10.1002/chem.201500707 ◽

2015 ◽

Vol 21 (39) ◽

pp. 13569-13576 ◽

Cited By ~ 20

Author(s):

Soichi Yokoyama ◽

Takashi Hirose ◽

Kenji Matsuda

Keyword(s):

Hydrogen Bonds ◽

Chain Length ◽

Self Assembly ◽

Alkyl Chain ◽

Pyrolytic Graphite ◽

Alkyl Chain Length ◽

Highly Oriented Pyrolytic Graphite

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Redox-sensitive reversible self-assembly of amino acid–naphthalene diimide conjugates

Interface Focus ◽

10.1098/rsfs.2016.0099 ◽

2017 ◽

Vol 7 (6) ◽

pp. 20160099 ◽

Cited By ~ 6

Author(s):

Wathsala Liyanage ◽

Paul W. Rubeo ◽

Bradley L. Nilsson

Keyword(s):

Amino Acid ◽

Self Assembly ◽

Functional Materials ◽

Supramolecular Materials ◽

Responsive Materials ◽

Naphthalene Diimide ◽

Reducing Conditions ◽

Aqueous Solvent ◽

Stimulus Responsive ◽

Fibril Aggregates

Peptide and low molecular weight amino acid-based materials that self-assemble in response to environmental triggers are highly desirable candidates in forming functional materials with tunable biophysical properties. In this paper, we explore redox-sensitive self-assembly of cationic phenylalanine derivatives conjugated to naphthalene diimide (NDI). Self-assembly of the cationic Phe-NDI conjugates into nanofibrils was induced in aqueous solvent at high ionic strength. Under reducing conditions, these self-assembled Phe-NDI conjugate fibrils underwent a morphological change to non-fibril aggregates. Upon reoxidation, the initially observed fibrils were reformed. The study herein provides an interesting strategy to effect reversible switching of the structure of supramolecular materials that can be applied to the development of sophisticated stimulus-responsive materials.

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Thermally bandwidth-controllable reflective liquid crystal film from rupture and self-assembly of hydrogen bonds

Liquid Crystals ◽

10.1080/02678292.2016.1197976 ◽

2016 ◽

Vol 43 (12) ◽

pp. 1732-1738 ◽

Cited By ~ 1

Author(s):

Feifei Wang ◽

Ping Song ◽

Huai Yang ◽

Xibin Shao

Keyword(s):

Liquid Crystal ◽

Hydrogen Bonds ◽

Self Assembly ◽

Crystal Film

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Synthesis of poly[(decanoic acid)-block-styrene] diblock copolymers and their self-assembly behavior in aqueous medium

Polymer International ◽

10.1002/pi.2120 ◽

2008 ◽

Vol 57 (4) ◽

pp. 571-576 ◽

Cited By ~ 4

Author(s):

Dongshuang Li ◽

Ke Sha ◽

Yapeng Li ◽

Peng Ai ◽

Xiaotian Liu ◽

...

Keyword(s):

Aqueous Medium ◽

Self Assembly ◽

Diblock Copolymers ◽

Decanoic Acid ◽

Assembly Behavior

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Dynamic porous property in a new heterometallic supramolecular compound

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314085258 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C1474-C1474

Author(s):

Patrice Kenfack ◽

Emmanuel Wenger ◽

Slimane Dahaoui ◽

John Lambi ◽

Pierrick Durand ◽

...

Keyword(s):

Hydrogen Bonds ◽

Self Assembly ◽

Water Clusters ◽

Chair Conformation ◽

Unit Cell ◽

Supramolecular Compounds ◽

Multifunctional Compounds ◽

Potential Applications ◽

One Step ◽

Mean Vector

Supramolecular compounds have attracted considerable interest to chemists, physicists and materials scientists due to their fascinating structures and potential applications as porosity [1-3] but one of the most appealing aims today, is to build multifunctional compounds. We are interested to rationalize the synthesis of porous heterometallic compounds by self- assembly via hydrogen bonds. In this communication, we present a stacked 2D Catena-{Co(amp)3Cr(ox)3.6H2O} (amp = 2-picolylamine, ox=oxalate). It is built by layers in which both (Co(amp)3+ (D) and Cr(ox)3- ( A)) ionic units are linked in a repeating DADADA...pattern along both the a and c axis with four and two hydrogen bonds respectively. These layers host very well resolved dodecameric discrete ring water clusters (R12) built by six independent molecules located around the centrosymmetric Wyckoff position's of the P21/n space group in which the compound crystallizes. The clusters are ranged along the [001] direction, occupy 807.6 Å3 (23.9%) of the unit cell and have a chair conformation via 10 hydrogen bonds. The dehydration process of the compound occurs in one step around 77oC and the dehydrated compound remains crystalline although all framework atoms move by 2.25 Å along a mean vector (dm= 2.21 i + 0.17 j + 0.37 k) during the process. The unit cell is then reduced by 12.34 % along a, 12.22% along b and 2. 03% along c reducing V by 22.03%. By exposure to air, the regeneration of the compound needs 90 min, following the first kinetic Avrami's model.

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Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bonds

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229617012979 ◽

2017 ◽

Vol 73 (10) ◽

pp. 820-827 ◽

Cited By ~ 8

Author(s):

Mikhail E. Minyaev ◽

Ilya E. Nifant'ev ◽

Alexander N. Tavtorkin ◽

Sof'ya A. Korchagina ◽

Shadana Sh. Zeynalova ◽

...

Keyword(s):

Rare Earth ◽

Hydrogen Bonds ◽

Crystal Structures ◽

Self Assembly ◽

Pentagonal Bipyramid ◽

Crystallographic Axis ◽

Nitrate Anion ◽

Two Dimensional ◽

Space Group ◽

Intramolecular Hydrogen

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]chloridotetrakis(methanol-κO)neodymium methanol disolvate, [Nd(C24H34O4P)Cl(CH4O)4]·2CH3OH, (1), and of the lutetium, [Lu(C24H34O4P)Cl(CH4O)4]·2CH3OH, (2), and yttrium, [Y(C24H34O4P)Cl(CH4O)4]·2CH3OH, (3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)phosphate and LnCl3(H2O)6 (in a 2:1 ratio) in methanol. Compounds (1)–(3) crystallize in the C2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl)phosphate ligands all display a κ1 O-monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O2P(O-2,6-iPr2C6H3)2}2Cl(CH3OH)4] molecular unit exhibits two intramolecular O—H...O hydrogen bonds, forming six-membered rings, and two intramolecular O—H...Cl interactions, forming four-membered rings. Intermolecular O—H...O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two-dimensional hydrogen-bond network. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]tetrakis(methanol-κO)(nitrato-κ2 O,O′)neodymium methanol disolvate, [Nd(C24H34O4P)(NO3)(CH4O)4]·2CH3OH, (4), have been obtained in an analogous manner from NdCl3(H2O)6. Compound (4) also crystalizes in the C2/c space group. Its crystal structure is similar to those of (1)–(3). The κ2 O,O′-bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CNNd = 8). Unlike (1)–(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the phosphate ligand and the NO3 − ligand. The structure of (4) displays intra- and intermolecular O—H...O hydrogen bonds similar to those in (1)–(3). Compounds (1)–(4) represent the first reported mononuclear bis[bis(diaryl/dialkyl)phosphate] rare-earth complexes.

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