Self-assembly of Bis[2-(2-hydroxyphenyl)-pyridine]Copper(Ⅱ) Induced by C-H…π and π…π Stacking Interaction

Introduction The control of molecular assembly in the solid state is an important theme of modern chemistry.It is in this regard that there is an activity in the area of supramolecular structures at present.The self-assembly of molecules can form well-defined supramolecular structures under the influence of drive forces such as hydrogen bonds[1-3],metal-ligand coordination bonds[4-6] and π…π stacking interactions[7-10].Word et al.have described the co-ordination chemistry of polydentate chelating ligands which contain mixed pyridine-phenol donor sets[11].Some unusual structures of transition metal pyridine-phenol complexes have been established in which non-covalent interactions such as hydrogen bonding and π…π stacking appear to play a dominant part.These observations suggest that it might be possible to construct supramolecular structures with a metal pyridine-phenol system.To explore this idea we have begun to investigate the self-assembly properties of metal pyridine-phenol complexes.Herein we present the self-assembly properties of Cu(pp)2[pp=2-(2-hydroxyphenol)-pyridine] under different conditions.     

π—πStacking Force in the Solid Structure of Mixed—Metal complexes：Zn（phen）2MS4（M=W,Mo）

1 INTRDUCTION Supramolecular chemistry of coordination compounds is the subject of intense research in recent years[1a]. Besides covalent bond, some weaker intermolecular interactions such as S…S con- tacts[1b], weak coordination, hydrogen bonding and pp stacking[1c] are efficient organising forces in supramolecular architecture. The properties of solid state materials may be quite different from those of isolated molecule due to the intermolecular interaction. In previous work[1d], we …     

An interlocked coordination cage based on aromatic amide ligands

An interlocked M_4 L_8 coordination cage was synthesized by coordination-driven self-assembly of palladium(Ⅱ) ions with aromatic amide bidentate ligands.The reaction of the ligand and the metal at 2:1 ratio led to the monomeric M_2 L_4 cage as the kinetic product,while the thermodynamic product M_4 L_8 cage was obtained by prolongating the reaction.This conve rsion and the interlocked structure was clearly revealed by using ~1 H NMR,mass spectrometry and X-ray crystallography.The driving force of interlocking was mainly attributed to the interactions(hydrogen bonding,aromatic stacking and electrostatic interaction) arising from the aptitude of flexibility of the amide ligand.     

One-dimensional Copper(II) Complex Constructed with Nitrate Counter-anion as Bitopic Connector

The design and synthesis of supramolecular structures has become an area of intense research in recent two decades.By carefully choosing the ions and ligands,frameworks with interesting and desirable properties can be created1-2.Essence of supramolecular chemistry is the self-assembly process of diversified interactions,such as metal-ligand coordination,hydrogen bonding,π-πstacking,etc.In contrast to the well-studied metal ions and ligands,there are relatively few examples about anionic func…     

Research progress in cation-π interactions

Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.     

The open-close mechanism of M2 channel protein in influenza A virus:A computational study on the hydrogen bonds and cation-π interactions among His37 and Trp41

The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study,the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues,and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then,quantum chemistry calculations at the MP2/6-311G level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calcula-tion results indicate that the binding strength of the N-H···N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1,and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1(T-shaped interaction) or -12.3 kcal·mol-1(parallel stacking interaction). Thus,the calcu-lated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.     

Effect of hydrogen bonding and hydrophobic interaction on the formation of supramolecular hydrogels formed by L-phenylalanine derivative hydrogelator

A new hydrogelator,pyridinium bromide salt of N-6-bromohexanoyl-L-phenylamino octadecane,was synthesized.Supramo- lecular hydrogels can be formed through the self-assembly of this hydrogelator in water.In this work,D_2O was used instead of H_2O as solvent for FT-IR measurement due to the fact that it is impossible to obtain useful FT-IR information on the hydrogen bonding in water.The investigation of FT-IR and steady-state fluorescence indicated that the driving forces for the self-assembly were mainly hydrogen bonding and hydrophobic interaction.Based on the data of XRD and molecular modeling,the possible mechanism of the formation of hydrogelator aggregates was proposed.     

Near-Infrared-Emissive Self-assembled Polymers <Emphasis Type="Italic">via</Emphasis> the Implementation of Molecular Tweezer/Guest Complexation on a Supramolecular Coordination Complex Platform

Coordination-driven self-assembly strategy has demonstrated the efficiency and versatility to construct well-ordered supramolecular coordination complexes (SCCs) such as discrete metallacycles and metallacages.In recent years,it has aroused tremendous interest to build more complexed self-assembled structures via the implementation of additional non-covalent recognition motifs on the SCCs platform.In this work,we have successfully attained this objective,with the elaborate manipulation of non-interfering pyridine-Pt2+and molecular tweezer/guest complexation in a hierarchical self-assembly manner.The resulting SCCs-based linear supramolecular polymers exhibit intriguing NIR-emissive behaviors,primarily attributed to the presence of intermolecular Pt(Ⅱ)-Pt(Ⅱ) metal-metal interactions in the non-covalent tweezering structure.Hence,supramolecular engineering of multiple non-covalent interactions offers a feasible avenue toward functional materials with tailored properties.     

Near-Infrared-Emissive Self-assembled Polymers via the Implementation of Molecular Tweezer/Guest Complexation on a Supramolecular Coordination Complex Platform

Coordination-driven self-assembly strategy has demonstrated the efficiency and versatility to construct well-ordered supramolecular coordination complexes(SCCs) such as discrete metallacycles and metallacages. In recent years, it has aroused tremendous interest to build more complexed self-assembled structures via the implementation of additional non-covalent recognition motifs on the SCCs platform. In this work, we have successfully attained this objective, with the elaborate manipulation of non-interfering pyridine-Pt~(2+) and molecular tweezer/guest complexation in a hierarchical self-assembly manner. The resulting SCCs-based linear supramolecular polymers exhibit intriguing NIR-emissive behaviors, primarily attributed to the presence of intermolecular Pt(Ⅱ)-Pt(Ⅱ) metal-metal interactions in the non-covalent tweezering structure. Hence, supramolecular engineering of multiple non-covalent interactions offers a feasible avenue toward functional materials with tailored properties.     

Supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host–guest interactions

Supramolecular polymers constructed by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host-guest interactions have received increasing attention due to their elegant structures,outstanding properties,and potential applications.Hydrogen bonding endows these supramolecular polymers with good adaptability and reversibility,while macrocyclic host-guest interactions give them good selectivity and versatile stimuli-responsiveness.Therefore,functional supramolecular polymers fabricated by these two highly specific,noninterfering interactions in an orthogonal way have shown wide applications in the fields of molecular machines,electronics,soft materials,etc.In this review,we discuss the recent advances of functional supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydroge n bonding and host-guest interactions.In particular,we focus on crown ether-and pillar[n]arene-based supramolecular polymers due to their compatibility with multiple hydrogen bonds in organic solution.The fabrication strategies,interesting properties,and potential applications of these advanced supramolecular materials are mainly concerned.     

Synthesis and Crystal Structure of Co(DMSO)_2(H_2O)_2(SCN)_2 with One-dimensional Hydrogen-bonded Structure (DMSO = Dimethylsulfoxide)

1 INTRODUCTION The development of supramolecular complexes has recently attracted considerable attention due to the fundamental interest in self-assembly processes of transition-metal complexes, supramolecular che- mistry and crystal engineering[1]. The ultimate goal is to gain control in order to direct their function[2]. Self-assembly through coordination and nonco- valent interactions such as hydrogen bonds, aromatic π···π stacking, steric repulsion and Van der Waals forces leads …     

Molecular and Supramolecular Structures of a Nickel（Ⅱ） Complex with a Macrocyclic Ligand

1 INTRODUCTION The knowledge of all non-covalent interactions, such as strong and weak hydrogen bonds and p…p interactions, is important to the supramolecular chemistry, biochemistry, crystal engineering and material science[1～7]. Several mononuclear complexes of macrocyclic oxamido Schiff base ligands with phenyls have been used as 揷omplex ligands?to design polynuclear complexes[8～11]. Herein we report the molecular and crystal structures, CH贩稯 hy- drogen bonding and p…p stacki…     

Advances on supramolecular assembly of cyclometalated platinum(Ⅱ) complexes

Organoplatinum(Ⅱ) compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum(Ⅱ) complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.     

Conjugated radical cation dimerization-driven generation of supramolecular architectures

The application of the homodimerization of the tetrathiafulvalene and 4,4‘-dipyridinium radical cation as a non-covalent driving force in supramolecular self-assembly has beensummarized.     

Synthesis and Crystal Structure of Trans-diaquabis(hexamethylenetetramine-N)bis(isothiocyanato)cobalt(Ⅱ) trans-tetraaquabis(isothiocyanato)cobalt(Ⅱ) dihydrate

1 INTRODUCTION Supramolecular compounds assembled by coordination covalent bonding or hydrogen bonding are of considerable interest due to their potential applications in developing new materials with magnetic, optical and catalytic properties[1]. One of the synthesis methods used to construct the functional compounds is that octahedral metal ion connects to polydentate ligand such as 4, 4?bipyridine, pyrazine and so on to form multi-dimensional supramolecular polymer[2]. Hmt (hexamethyl…     

A Novel Silver(Ⅰ) σ-Complex Supramolecular Polymer: [Ag_2(σ-HOPhCO_2)_2]_n

Introduction Supramolecular chemistry may be defined as 揷hemistry beyond the molecule?bearing on the organized entities of higher complexity resulting from the association of two or more chemical species held together by intermolecular non-covalent forces, including hydrogen bond, electrostatic interaction, van der Waals force and short-range exclusion force, etc.1 Supramolecular compounds with special structures and functions have wide application in various fields such as material, catalysi…     

Mechanism of N-octadecyl-N1-maleoyl-L-phenylalanine self-assembled into supramolecular structures

N-Octadecyl-N1-maleoyl-L-phenylalanine （ODMA-L-Phe） was synthesized through the condensation, deprotection and acid- ylation reaction of BOC-L-phenylalanine, octadecylamine and maleic anhydride. ODMA-L-Phe can self-assemble in some organic solvents and turned them into thermally reversible physical supramolecular organogels. The morphology of ODMA-L-Phe aggregates was characterized by polarized optical microscopy （POM） and field emission scanning electron microscope （FE-SEM）. The aggregates of ODMA-L-Phe were needle-like fibrils with diameters of approximately 100-200 nm. The mechanism of ODMA- L-Phe self-assembly in organic solvents was investigated using XH NMR and circular dichroism （CD）. The results indicated that hydrogen bonding was one of the main driving forces for the self-assembly of ODMA-L-Phe.     

Mechanism of N-octadecyl-N′-maleoyl-L-phenylalanine self-assembled into supramolecular structures

N-Octadecyl-N′-maleoyl-L-phenylalanine(ODMA-L-Phe)was synthesized through the condensation,deprotection and acid- ylation reaction of BOC-L-phenylalauine,octadecylamine and maleic anhydride,ODMA-L-Phe can self-assemble in some organic solvents and turned them into thermally reversible physical supramolecular organogels.The morphology of ODMA-L-Phe aggregates was characterized by polarized optical microscopy(POM)and field emission scanning electron microscope(FE-SEM). The aggregates of ODMA-L-Phe were needle-like fibrils with diameters of approximately 100-200 nm.The mechanism of ODMA- L-Phe serf-assembly in organic solvents was investigated using ~1H NMR and circular dichroism(CD).The results indicated that hydrogen bonding was one of the main driving forces for the self-assembly of ODMA-L-Phe.     

Syntheses and Br…π supramolecular interactions in the crystal structure of ipriflavone bromides

Supramolecular forces, including electrostatic in- teraction, hydrogen bond, hydrophobic interaction and aromatic stacking interaction, are the important re- search area in supramolecular chemistry and crystal engineering[1]. Aromatic stacking interaction…     

Supramolecular Polymer Emulsifiers for One-step Complex Emulsions

Complex emulsions,such as double emulsions and high-internal-phase emulsions,have shown great applications in the fields of drug delivery,sensing,catalysis,oil-water separation and self-healing materials.Their controllable preparation is at the forefront of interface and material science.Surfactants and polymers have been widely used as emulsifiers for building complex emulsions.Yet some inherent disadvantages exist including multi-step emulsifications and low production efficiency.Alternatively,supramolecular polymer emulsifier for complex emulsions via one-step emulsification is rising as a new strategy due to the ease of preparation.In this feature article,we review our recent progresses in using supramolecular polymer emulsifiers for the preparation of complex emulsions.Double emulsions and high-internal-phase emulsions are successfully prepared via one-step emulsification with the help of different supramolecular interactions including electrostatic,hydrogen bond,coordination interaction and dynamic covalent bond,which will be particularly emphasized in detail.In the end,a comprehensive prospect is given for the future development of this field.This article is expected to provide new inspirations for preparing complex emulsions via supramolecular routes.