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.

Synthesis and Crystal Structure of a Macrocycle[Cu(dadm)(mal)(H_(2)O)]_(2)·2H_(2)O

The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?

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.

Synthesis and Crystal Structure of a New Macrocycle Based on Diethoxycarbonyl Glycoluril: C_(26)H_(30)N_6O_(10)

A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.

The Synthesis and Structure of Adduct of a New Schiff Base Macrocycle with Two THF：THIONE2B4［36］ENE－O6N8·2THF

New Schiff base Macrocyclic compound of 2,3: 11, 12:20, 21:29, 30-tetrabenzo-1,13,16,19,31,34-hexaoxa-5,6,8,9,23,24,26,27-octaaza-7,25-dithione-2,3:4,5:9,10:11,12:22, 23:27,28:29,30 cyclo-[36]ene (thione2B4[36] ene-O6N8) containing THF has been prepared. It crystallizes in the monoclinic, space group P21/n. with parameters a=9.829(5) b=24.23(1), c=10.181(9), β=92.93(5)°, Z=2, V=2422(3)3, Dc=1.25gcm-3. Data collection: Rigaku AFC-5R diffractometer,(MoKα, λ=0.71069), ω /2θ scans. θmax=25°, empirical absorption correction, 4658 measured reflections, 4387 independent, 1743 observed reflections [I≥3σ(I)]. The final R=0.056. RW=0.069,S=1 .54, (Δ/σ)max=0.01,Δρmax=0.36e-3.

Proton-Template Synthesis of a П─Conjugated Macrocycle and Structure of its Ni_2(Ⅱ)—Complex

metol-free Robson -type macrocycle was synthesized for first time by proton-templation and from that the metal complexes were prepared.By X-ray study the structure of Ni(Ⅱ)-complex was characterized.

A NOVEL THIOPHENE-DERIVED N_2O_2 MACROCYCLE AND ITS Ag(I) COMPLEX: SYNTHESIS AND CHARACTERIZATION

A novel macrocycle containing thiophene （L） was prepared first by the interaction of 2,5-bis-（chloromethyl）-thiophene （A） and salicylaldehyde to give 2, 5-bis-（2-formylphenoxymethyl）-thiophene （B）, and then by the nontemplate cyclocondensation of 1,3-diaminopropane with （B） followed by a "onepot" reduction without isolation of the diimine intermediate. The corresponding silver complex, AgLClO;, was also prepared. The macrocycle was characterized by IR, elemental analysis, MS and;HNMR.

Synthesis and Crystal Structure of a Novel 1D Mercury(II) Iodide Coordination Polymer Containing 40-Membered Macrocycle

A mercury coordination polymer [Hg3（TizT）216]n （Mr = 1921.72, TizT = 2,4,6- tri（imidazole- 1-yl）- 1,3,5-triazine） containing a 40-membered macrocycle which was constructed by four TizT ligands and four mercury（II） iodide molecules had been synthesized by the reaction of HgI2 with TizT. The complex was characterized by elemental analysis, FT-IR, ^1H NMR spectra and X-ray crystallography. The crystal of the complex belongs to the monoclinic system and C2/c space group with a = 35.840（5）, b = 8.169（5）, c = 14.980（5） A, β = 104.466（5）°, Z= 4, V= 4247（3） A^3, De = 3.006 g·cm^-3, μ= 15.223 mm^-1, F（000） = 3384, Rint = 0.0504, wR = 0.0833 and constructs a chair-like conformation of cyclohexane one by one, which forms a 1-D polymer through the fashion of fused ring aromatic hydrocarbon. The hydrogen bonds and π-π interactions shape the 2-D network structure. The two compounds excited weak fluorescence.

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.

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.

THE LINEAR CORRELATIONS BETWEEN ELECTRONIC TRANSITION ENERGY AND HAMMETT CONSTANTS FOR THE SUBSTITUTED PORPHYRIN-LIKE MACROCYCLE

The properties of absorption spectra are presented and the linear correlations of Hammett constants with the 0-0 transition energy(E_(o,o))of S_←S_o, and the ratios of oscillator strength(f/f)are used to probe the interactions betwee π-electron of aromatic maerocycles or metal ion of complexes with the sub- stituents on β-position of benzene ring for porphyrin-like maerocyclic compounds.

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.

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 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.

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 and Crystal Structure of a Novel Bis(ethoxycarbonyl)glycoluril Macrocycle

A novel [2＋4＋2]-macrocyclic compound 3（C52H69N16O12, Mr = 1109.53） con- taining bis（ethoxycarbonyl）glycoluril groups was synthesized via the Mannich three-component reaction in one pot and its structure was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.077（3）, b = 10.642（3）, c = 15.324（5） , α = 96.704（5）, β = 102.304（5）, γ = 104.546（5）°, Z = 2, V = 1528.7（8）3, Dc = 1.283 g/cm3, μ = 0.097 mm-1, F（000） = 628, R = 0.0818 and wR（I 〉 2σ（I）） = 0.2346 for 3034 observed reflections.

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.

Bioinspired supramolecular macrocycle hybrid membranes with enhanced proton conductivity

Enhancing the proton conductivity of proton exchange membranes(PEMs)is essential to expand the applications of proton exchange membrane fuel cells(PEMFCs).Inspired by the proton conduction mechanism of bacteriorhodopsin,cucurbit[n]urils(CB[n],where n is the number of glycoluril units,n=6,7,or 8)are introduced into sulfonated poly(ether ether ketone)(SPEEK)matrix to fabricate hybrid PEMs,employing a nature-inspired chemical engineering(NICE)methodology.The carbonyl groups of CB[n]act as proton-conducting sites,while the host–guest interaction between CB[n]and water molecules offers extra protonconducting pathways.Additionally,the molecular size of CB[n]aids in their dispersion within the SPEEK matrix,effectively bridging the unconnected proton-conducting sulfonic group domains within the SPEEK membrane.Consequently,all hybrid membranes exhibit significantly enhanced proton conductivity.Notably,the SPEEK membrane incorporating 1 wt.%CB[8](CB[8]/SPEEK-1%)demonstrates the highest proton conductivity of 198.0 mS·cm^(−1) at 60°C and 100%relative humidity(RH),which is 228%greater than that of the pure SPEEK membrane under the same conditions.Moreover,hybrid membranes exhibit superior fuel cell performance.The CB[8]/SPEEK-1%membrane achieves a maximum power density of 214 mW·cm^(−2),representing a 140%improvement over the pure SPEEK membrane(89 mW·cm^(−2))at 50°C and 100%RH.These findings serve as a foundation for constructing continuous proton-conducting pathways within membranes by utilizing supramolecular macrocycles as fuel cell electrolytes and in other applications.