Synthesis of Schiff Base Type Macrocycles Containing Naphthalene Ring

A series of new Schiff base type macrocyclic crown ethers containing naphthalene ring were synthesized from 2,2'-di(o-formylnaphthoxy) ethyl ether or 1,2-di(o-formylnaphthoxy) ethane and four appropriate diamines. The chemical structures of the new compounds were characterized by elemental analysis, infrared spectra, nuclear magnetic resonance spectra and mass spectrometry.

THE SYNTHESIS AND CHARACTERIZATION OF ASYMMETRIC TRIPYRRANE-CONTAINING MACROCYCLES

An improved procedure was used to prepare the asymmetric tripyrrane-containing macrocycles, The yield was over 85% These maerocycles could be oxidized to the methine bridled 23 (?)-electron aromatic cadmium(Ⅱ)complexes by reating with cadmium chloride in the presence of air and their atructures were characterized.

PHOTOPHYSICAL PROPERTIES OF THE ASYMMETRIC PENTAAZADENTATE PORPHYRIN-LIKE MACROCYCLES

The porphyrin-like macrocycles and their metal complexes are s novel family of photoresponsive molecules.The properties of the excited states,both singlet and triplet are investigated by the stationary and transient processes.

Synthesis and Mesophase Properties of Intraanular Functionized Shape-persistent Macrocycles Containing Dibenzo[fg,op]naphthacenes

On the basis of the C-C coupling reactions of dibenzo [ fg, op ] naphthacene bistriflate, which was obtained by the condensation of phenylacetates with 4-aryl-2,6-bis（2-bromo-4-methoxy-phenyl） pyrylium salts followed by palladium-catalyzed dehydrohalogenation, three shape-persistent macrocycles with dibenzonaphthacene corner pieces, a nanometer interior void, and intraanular oligoalkyl side groups were synthesized by the oxidative cyclization of the corresponding bisacetylenes under high-dilution conditions. Their thermotropic liquid crystalline properties were investigated by using polarizing microscopy and differential scanning calorimetry. All the three compounds showed nematic mesophases and belonged to discotic liquid crystals with inverted topology.

Synthesis and Electrical Conductivities of Fully Conjugated Schiff Base Macrocycles Containing 1,3,4-Oxadiazole

Conjugated Schiff base macrocycles containing 1,3,3-oxadiazole were prepared by [2 + 2] cyclic condensation of phenylenediamine with 2,5-bis(m-formyl-phenyl)-1,3,4-oxadiazole. These macrocycles with iodine or TCNQ produced stable charge-transfer complexes. The formation of complexes were identified by UV-Vis and FT-IR spectra.

Synthesis of Macrocycles Containing Amino Acid Ester and Aryl-heterocyclic Units

Four kinds of new macrocycles containing amino acids and nyl-heterocyclic units were synthesized by the condensation of di-esters containing Ts-amino acids units with di-halogenated compounds at room temperature. The macrocycles were characterized by elemental analysis, IR,MS(FAB) and 1H NMR

SYNTHESIS OF AZA-OXA MACROCYCLES CONTAINING PYRIDINE RING

A new type of aza-oxa macrocycles containing pyridine ring which may be used for binding of prinary ammonium cations(R-NH) were prepared from 2.6-di(bromomethyl) pyridine and appropriate diol.

Studies on the Protonation and Complexations of Dioxotetraamine Macrocycles

14-Membered macrocyclic dioxotetraamines deprotonate stepwisely upon coordination to cupric ions. Singly- and doubly-deprotonated complexes are the main species, While for 13-membered analogs, non- and doubly-deprotonated complexes are the main species.

Synthesis of phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups

Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.

Construction of a Self-assembling Intertwined Spiral Solvent Channel Based on Interactions between Macrocycles and CH_2Cl_2

The construction of an unprecedented intertwined spiral solvent channel is driven by weak C–Cl…O and C–H…N interactions based on extraordinary parallel spirals which were structured from supramolecular synthon macrocycle 1（C44H44N4O4） with a propargylamine backbone. The product is characterized by ^1H NMR, ^13C NMR, IR and HRMS, and further confirmed by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 28.922（3）, b = 8.5069（9）, c = 21.687（2）A^°, β = 130.6320（10）°, V = 4049.4（7） A^°3 and Z = 8. A total of 11874 reflections were collected, of which 4942 were independent（Rint = 0.0590） and 2937 were observed with I 〉 2σ（I）. The final full-matrix least-squares refinement gave R（I 〉 2s（I）） = 0.069 and w R = 0.167, S = 1.05,（Δρ）max = 0.20 and（Δρ）min =-0.22 e·A^1-3. The fluorescence of the product is discussed.

Recent applications of macrocycles in supramolecular catalysis

Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic structure and modified functional groups of these macrocycles can influence substrate and transition state stability, as well as reaction selectivity. The inner cavities of these macrocycles are particularly beneficial, as they enable substrates to adopt preorganized arrangements and serve as versatile platforms for highly efficient supramolecular catalytic systems. This minireview provides an overview of recent advancements in supramolecular catalysis using various macrocycles, such as crown ethers, cyclodextrins,calixarenes, pillararenes, cucurbiturils, and other novel macrocycles.

Amide naphthotubes:Biomimetic macrocycles for selective molecular recognition

Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments.By mimicking the cavity feature of bioreceptors,Prof.Wei Jiang proposed and clarified the concept of“endo-functionalized cavity”.Through situating polar binding sites into a deep hydrophobic cavity,we designed and synthesized several macrocyclic hosts,among which amide naphthotubes are the most representative.The hosts can selectively recognize various polar molecules including organic micropollutants,drug molecules,and chiral molecules in water by employing the hydrophobic effect and shielded hydrogen bonding.In addition,these biomimetic hosts have been applied in spectroscopic analysis,adsorptive separation and self-assembly.In this review,we provide an overview of recent advances on amide naphthotubes with special emphasis on the efforts of Jiang's group.We are convinced that these biomimetic macrocycles will make further contributions to supramolecular chemistry and beyond.

Synthesis and applications of lanthanoid complexes of pentadentate and hexadentate N_(5) and N_(6) macrocycles:A review

In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.

Photoactive donor-acceptor conjugated macrocycles:New opportunities for supramolecular chemistry

The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D-A)conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties.In addition,the well-defined cavities in such D-A macrocycles endow them with versatile host-guest properties.In this review,we provide a comprehensive summary of D-A conjugated macrocycle chemistry,detailing recent progress in the area of synthetic methods,optical properties,host-guest chemistry and applications of the underlying chemistry to chemical sensors,bioimaging and photoelectronic devices.Our objective is to provide not only a review of the fundamental findings,but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.

Chiral selection of Troger's base-based macrocycles with different ethylene glycol chains length in crystallization

In the present work,two Troger's base-based macrocycles(TBBMs)with different bridging ethylene glycol chains(T1,n=1;T3,n=3)were successfully synthesized and studied via the crystal analysis.These two TBBMs possess rare rectangular-like cavities and show chiral selection during the crystallization.T1with short glycol chain(n=1)crystallized as racemates,while T3 with long glycol chain(n=3)was found as meso isomer.In contrast to T1 and T3,for T2(n=2)both rac-T2 and meso isomer R2NS2N-T2has been observed in our previous report.Thus,the synthesis of new TBBMs T1 and T3 with different bridging ethylene glycol chains not only makes the study of TBBMs more systematically,but also helps to understand the relationship between the size of the rectangular cavity and the chiral selection of Troger's base-based macrocycles during their crystallization.

Facile synthesis of azobenzene-embedded conjugated macrocycles for optically switchable single-crystal transistors and tunable supramolecular assemblies

A series of newπ-conjugated macrocycles(AzoM-n-E,n 1–3)incorporating=azobenzene units have been synthesized by a facile strategy in one-pot reaction.The resultant azobenzene-embedded macrocycles feature intrinsic photoresponsive behaviors and intriguing supramolecular assembling properties.The smallest macro-cycle AzoM-1-E with a rigid planar conjugated backbone structure is used to prepare the single crystal transistors,showing reversible optical tunability.The moderate size macrocycle AzoM-2-E assembles into a dimer in the form of interpenetration throughπ-πstacking between azobenzene units.The largest macrocycle AzoM-3-E with enhancedflexibility can adaptively assemble with various types of electron-deficient guests accompanied by distortion of azobenzene.Typically,AzoM-3-E assembles with the planar F4-TCNQ to form a tetragonal geometry by C-F⋅⋅⋅π and π-π interactions,while the assembly with ellipsoidal C70 viaπ-πinteractions induces AzoM-3-E to form a boat-shaped geometry.This work will shed new light on the development of functional conjugated macrocycles in organic electronics.

Selenium containing macrocycles:transformation between Se-N/Se-S/Se-Se bonds

Macrocycles possess potential applications in supramolecular chemistry and biosystems.Thus development of new kinds of macrocycles is of significance.Herein,novel macrocycles containing Se-Se/Se-S bonds were synthesized via transformation between selenium related dynamic covalent bonds.A monomer containing two ebselen moieties was synthesized(M1).The Se-N bonds in M1 were reduced by dithiothreitol,forming Se-S linked dimer(D1).To realize the transformation from Se-S bonds to Se-Se bonds,guest molecules were added as template,triggering the formation of Se-Se linked dimer(D2).The formation of these two new kinds of macrocycles was determined by ~1H NMR and ^(77)Se NMR,and the necessity of guest molecules was also confirmed.The introduction of ebselen moieties and Se-S bonds or Se-Se bonds into macrocycles may endow it with new responsiveness and bioactivities,as well as new types of host-guest chemistry.

Gold nanoparticles functionalized with supramolecular macrocycles

Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we summarize the recent research progress on the synthesis and assembly of AuNPs functionalized with different supramolecular macrocyclic compounds, i.e., crown ethers, cyclophanes, cyclodextrins （CDs）, cucurbit[n]urils （CB[n]）, calix[n]arenes, and pillar[n]arenes （PIn]A）. Meanwhile, applications of these supramolecular hybrid nanomaterials in the fields of sensors, biomedicine and plasmonic devices are also presented.

Synthesis of Donor-Acceptorπ-Conjugated Macrocycles by Post-Functionalization

Main observation and conclusion In this paper,two novel donor-acceptor(D-A)macrocyclic compounds 5 and 7 were successfully synthesized by post-functionalization of a planar dimer macrocycle(1)and a highly twisted trimer macrocycle(2),respectively,via controllable oxidation of methoxy groups and condensation between diketones and phenylenediamine in succession.Compared with unembellished 9,10-dimethoxyphenanthrene,the resultant dibenzo[a,c]phenazine motif is electron-deficient rather than electron-rich,yielding two D-Aπ-conjugated macrocycles with more contractive energy gaps.Density functional theory(DFT)calculations further support the unequivocal evidence of the D-A properties of macrocycles 5 and 7.The difference of their photophysical properties was investigated by the aid of ultraviolet-visible absorption and fluorescence spectrophotometers.Furthermore,the stacking patterns of 7 and its contrastπ-conjugated macrocycle trimer(2)were compared via the analysis of X-ray single crystal,in which the electron-deficient dibenzo[a,c]phenazine unit provides extra interaction sites,resulting in orderly arrangement of 7 in the solid state.