5-aminoisophthalic Acid Research Articles

Synthesis, structures and photoluminescence of three d10 5-aminonicotinate and 5-aminoisophthalate coordination polymers with bilayer structures

Base on ligands 5-aminonicotinic acid and 5-aminoisophthalic acid, three novel d10 coordination polymers [Zn(ant)2]n (Zn-ant) (ant=5-aminonicotinate anion), [CdBa(aip)2(H2O)2]n (CdBa-aip) and [Cd3(aip)2(C2O4)(H2O)6]n (Cd-aipox) (aip=5-aminoisophthalate anion) are obtained by hydrothermal reactions, and characterized by means of FT-IR spectra, elemental analysis, single-crystal X-ray diffraction analysis and X-ray powder diffraction techniques. Thermogravimetric analysis is also carried out in order to investigate the stability of compounds Compound Zn-ant exhibits a 2D interlaced-bilayer structure. While compounds CdBa-aip and Cd-aipox feature the unusual 2D pillared-bilayer structures formed by the cross-linking of the aip and oxalate units. Considering the complicated hydrogen bonds and interlayer π⋯π stacking interactions, all of the three compounds are finally packed into three-dimensional supramolecular networks. The deprotonating reagent-induced effect is responsible for the generation of two different compounds CdBa-aip and Cd-aipox. In addition, the photoluminescent properties of three compounds have also been investigated in the solid state at room temperature.

A rhodamine B-based fluorescent sensor toward highly selective mercury (II) ions detection

This work presented the design, syntheses and photophysical properties of a rhodamine B-based fluorescence probe, which exhibited a sensitive and selective recognition towards mercury (II). The chemosensor RA (Rhodamine- amide- derivative) contained a 5-aminoisophthalic acid diethyl ester and a rhodamine group, and the property of spirolactone of this chemosensor RA was detected by X-ray crystal structure analyses. Chemosensor RA afforded turn-on fluorescence enhancement and displayed high brightness for Hg2+, which leaded to the opening of the spirolactone ring and consequently caused the appearance of strong absorption at visible range, moreover, the obvious and characteristic color changed from colorless to pink was observed. We envisioned that the chemosensor RA exhibited a considerable specificity with two mercury (II) ions which was attributed to the open of spirolactone over other interference metal ions.

Effect of organic dicarboxylate on the self-assembly of ternary mixed-ligand cobalt(II) coordination polymers: Syntheses, fluorescence and catalytic properties

Two Co(II) coordination polymers, formulated as [Co(bix)(tbta)]n (1) and [Co(bix)0.5(aip)(H2O)]n (2) (bix=1,4-bis(imidazol-1-ylmethyl)benzene, H2tbta=tetrabromoterephthalic acid, H2aip=5-aminoisophthalic acid) have been synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 features a 3D three-fold interpenetrating diamond framework. Complex 2 is a 2D (3,4) network with 3,4L83 topology and extend into an unusual (5,6)-connected 3D supramolecular framework via intermolecular hydrogen bonds. In addition, fluorescence and catalytic performances of complexes 1 and 2 for the degradation of Congo red dye in a photo-Fenton-like process were investigated.

Organotin(IV) complexes with 5-aminoisophthalic acid: Synthesis, characterization, theoretical study, and biological activities

Organotin(IV) carboxylates with the general formula [Bu2(Cl)Sn]2L (1), (Me3Sn)2L (2), and (Bu3Sn)2L (3) were synthesized by stirring 5-aminoisophthalic acid with KOH in methanol and with following addition of Bu2SnCl2/Me3SnCl/Bu3SnCl under stirring conditions. The complexes were characterized by the microanalysis, IR, and 1H NMR spectroscopies, mass spectrometry, and by the DFT and semi-empirical methods. The data on the elemental analysis and mass fragmentation agree well with the chemical composition of the complexes. The IR spectroscopy demonstrated a chelating coordination mode of the carboxylate group. The 1H NMR spectroscopy confirmed the 5-coordinated geometry of the organotin(IV) derivatives. The DFT and semi-empirical calculation of the complex 2 supported an asymmetric coordination behavior of the carboxylate group. The complexes 2 and 3 exhibited an intercalating binding with salmon sperm DNA. Significant antibacterial/antifungal potential of the complexes was confirmed by the disc diffusion method and evaluation of the minimum inhibitory concentration (MIC). The hemolytic activity of the complexes is higher than that of a free ligand and PBS and sufficiently lower than that of triton X-100.

Three 2 D copper(II)/cadmium(II) coordination polymers based on semi-rigid/flexible bis-pyridyl-bis-amide ligands and 5-aminoisophthalate: Syntheses, structures and properties

Three new transition metal coordination polymers [Cu(3-bpcb)0.5(5-AIP)] ⋅2H2O (1), [Cd(3-bpc b)0.5(5-AIP)(H2O)] ⋅H 2O (2) and [Cd(3-bpsa)0.5(5-AIP)(H2O)] ⋅2H2O (3) have been hydrothermally synthesized by self-assembly of 5-aminoisophthalic acid (5-H2AIP), semi-rigid or flexible bis-pyridyl-bis-amide ligands [3-bpcb = N N ′-bis(3-pyridinecarboxamide)-1,4-benzene, 3-bpsa = N,N ′-bis(3-pyridyl)succinamide], and copper chloride or cadmium nitrate. X-ray diffraction analysis reveals that compounds 1 and 2 possess similar 2 D double-layered structures with (3,4)-connected (63)(65⋅8) topology, while compound 3 displays a 2 D layer with {62.10}{6} topology. The adjacent layers of 1–3 are finally extended into 3 D supramolecular frameworks by hydrogen bonding interactions. The bis-pyridyl-bis-amide ligands with different flexibilities play an important role in the construction of final topological structures for the title compounds. Further, the electrochemical behavior of the compound 1 and the fluorescent and photocatalytic properties of compounds 1–3 have been investigated. Three new copper(II)/cadmium(II) coordination polymers have been hydrothermally synthesized by self-assembly of 5-H2AIP, semi-rigid or flexible bis-pyridyl-bis-amide ligands and copper chloride or cadmium nitrate. The electrochemical behavior, the fluorescent and photocatalytic properties of the compounds have been investigated.

Synthesis, structural characterization and microbial activity of 2D Ag(I)-5-aminoisophthalate coordination polymer with a new coordination mode

In this study, a novel polynuclear Ag(I)-5-aminoisophthalate complex [Ag(μ4-Haip)]n (1) (H2aip = 5-aminoisophthalic acid) has been synthesized. The molecular structure of this complex has been determined by the single crystal X-ray diffraction. The two-dimensional polynuclear complex is crystallized in the triclinic crystal system with space group P-1. The Ag(I) ion is four-coordinated by three carboxylate oxygen atoms of three different Haip ligands and one nitrogen atom in a distorted tetrahedral geometry. Furthermore, a novel coordination mode has shown by H2aip. This complex exhibits photoluminescence in the solid state at room temperature. Antimicrobial activity of complex was evaluated by the agar diffusion method. The complex showed antimicrobial activity against tested microorganism strains (Gram positive, gram negative bacteria, clinic isolate yeast and mold). Moreover this complex showed particularly high antifungal activity against yeast and mold.

ChemInform Abstract: Fluorous Bis(oxazolines) Ligand: Synthesis and Application in Kabachnik‐Fields Reaction.

Abstract A novel fluorous bis(oxazolines) ligand was synthesized with 70% overall yield in 5 steps starting from 5-aminoisophthalic acid. The ligand was applied in the one-pot synthesis of α-aminophosphonates via copper-catalyzed Kabachnik-Fields reaction, giving the corresponding products in moderate to excellent yields under mild conditions. Furthermore, the fluorous ligand could be easily recovered and reused for four times without significant loss of activity.

Synthesis and characterization of novel polyamides containing dibenzobarrelene pendant groups

The 5-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido) isophthalic acid (DEAIA) monomer, containing a dibenzobarrelene pendant group, was synthesized by the condensation of 5-aminoisophthalic acid and 9,10-dihydroanthracene-9,10-α,β-succinic anhydride (DASA). The DEAIA monomer was reacted with four structurally different aromatic diamines to synthesize four novel polyamides. All aromatic polyamide based in the DEAIA monomer showed very good solubility in aprotic polar solvents and excellent thermal stability with onset of decomposition at 430 °C. They readily form membrane by the casting method. Moreover, the most interesting polyamide was DEAIA-6F that showed high thermal stability, good film formation, and the largest gas permeability coefficients in comparison with a reported polyhexafluoroisophthalamide, HFAISO; this confirms the advantage of inserting a dibenzobarrelene pendant group.

Four new Mn(II) inorganic-organic hybrid frameworks with diverse inorganic magnetic chain's sequences: syntheses, structures, magnetic, NLO, and dielectric properties.

Four new inorganic-organic hybrid manganese frameworks, formulated as [Mn(Am-Hip)2]·3H2O (1), [Mn2(ip)2(H2O)]·CH3OH (2), [Mn2(OH-ip)2(DMF)]·DMF (3), and (Me2NH2)[Mn4(sdba)4(Hsdba)(H2O)]·3H2O·2DMF (4) (Am-H2ip = 5-aminoisophthalic acid, H2ip = isophthalic acid, OH-H2ip = 5-hydroxyisophthalic acid, and H2sdba = 4,4'-sulfonyldibenzoic acid), have been prepared by solvothermal reactions of Mn(II) ions with different polycarboxylate acids in the presence of LiNO3 or NH4NO3. Single-crystal X-ray diffraction studies reveal that the frameworks of 1-4 contain diverse Mn(II)-oxygen inorganic magnetic chain's sequences, -J1J1J1J1- for 1, -J1J2J1J2- for 2, -J1J1J2J2- for 3, and -J1J2J3J3- for 4. The sequence in 4 has never been seen for the magnetic chain compounds and is a new type of magnetic alternating sequence. Magnetic investigations indicate that these compounds all show weak antiferromagnetic couplings between the adjacent Mn(II) ions. Magnetostructural analyses based on the data of 1-4 and other related Mn(II) chain compounds imply that the magnitude of the magnetic coupling has some relationship with the Mn-O-Mn angle of the μ2-O bridge and the average Mn-O-C-O torsion angle of the carboxylate bridges. Compounds 2 and 4 crystallize in chiral and acentric space groups, and they both exhibit powder second harmonic generation (SHG) efficiencies approximately 0.6 and 0.9 times, respectively, that of the standard potassium dihydrogen phosphate (KDP) powder. In addition, the dielectric properties of 2 and 4 were also investigated.

Four heterometallic coordination polymers of a macrocyclic oxamide with aromatic multicarboxylate ligands: Syntheses, crystal structures and magnetic properties

Four new coordination polymers, [Mn(CuL)(aipt)] (1), [Ni(CuL)(aipt)(H2O)]·H2O (2), [Mn(NiL)(tpt)]·1/4H2O (3) and [Mn(NiL)(atpt)] (4) (ML, H2L=2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H2aipt=5-aminoisophthalic acid; H2tpt=terephthalic acid; H2aipt=2-aminoterephthalic acid), have been synthesized by a solvothermal method and their structures are characterized by single-crystal X-ray diffraction. Complex 1 exhibits a 1D chain structure formed by Cu2Mn2 units connected via oxamide and 5-aminoisophthalate bridges, while complexes 2, 3 and 4 exhibit different 2D layered structures formed by Cu2Ni2 (2) and Mn2Ni2 (3–4) units, connected via oxamide and diverse carboxylate bridges. Magnetic studies demonstrate that antiferromagnetic interactions exist between the neighboring metal ions through the oxamide and/or carboxyl bridges in complexes 1–4.

Poly (azo-ester)s: Interfacial Synthesis of Optically Active Polymers

(2S)-5-(3-Methyl-2-phthalimidylpentanoylamino)isophthalic acid (1), (2S)-5-(2-Phthalimidiylpropanoylamino) isophthalic acid, and (2S)-5-(3-phenyl-2-phthalimidylpropanoylamino)isophthalic acid were prepared from phthalic anhydride, 5-aminoisophthalic acid and the corresponding L-amino acids in acetic acid. The interfacial polycondensation of the corresponding diacid chlorides with two aromatic diazo containing diols such as 4,4’-[4,4’-diphenyl sulfonedi-diazene- 2,1-diyl] bis (phenol) and 4,4’-[4,4’-diphenyl etherdi-diazene-2,1-diyl] bis(phenol) were carried out at room temperature. Six novel optically active poly (azo-ester)s (PAE)s including phthalimide groups were obtained with good yields and inherent viscosities of 0.12-0.25 dLg-1. The new (PAE)s are readily soluble in organic solvents. The resulting polymers were characterized by specific rotation, FT-IR and 1H NMR spectroscopy, elemental analysis and thermo gravimetric analysis (TGA). Keywords: Optically active, poly (azo-ester), phthalic anhydride, L-amino acid, interfacial polymerization, diol.

Two New 3D Zn(II)/Cu(II) Coordination Polymers Based on N,N′-Di(3-pyridyl)succinamide and Two Different Aromatic Dicarboxylates: Syntheses, Crystal Structures and Properties

Two new 3D transition metal coordination polymers [Zn(1,3-BDC)(L)0.5] (1) and [Cu(5-AIP)(L)0.5] (2) [L = N,N′-di(3-pyridyl)succinamide, 1,3-H2BDC = 1,3-benzenedicarboxylic acid, 5-H2AIP = 5-aminoisophthalic acid] have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, TG and single crystal X-ray diffraction analysis. In complex 1, two carboxyl groups with monodentate modes from two 1,3-BDC ligands connect two Zn(II) ions to form a dinuclear {Zn2} SBUs, then the adjacent {Zn2} SBUs are connected by two pairs of 1,3-BDC ligands and two L ligands to construct a 3D coordination network with the large square-shape grids. Finally, the complex 1 exhibits a 4-connected CdSO4 topology with the threefold interpenetrating feature. Complex 2 is a 3D coordination framework constructed by the ligands L and 5-AIP anions, which represents a binodal (3,8)-connected {42·6}2{44·610·79·85} topology. The different coordination modes of metal ions and two dicarboxylates play important roles in the formation of coordination frameworks for title complexes. In addition, the thermal stabilities, the fluorescent properties of complexes 1–2 and the electrochemical behavior of complex 2 modified carbon paste electrode have also been investigated. Two new 3D coordination polymers, [Zn(1,3-BDC)(L)0.5] (1) and [Cu(5-AIP)(L)0.5] (2), have been hydrothermally synthesized. Complex 1 represents a threefold interpenetrating CdSO4 topology, complex 2 exhibits a binodal (3,8)-connected {42·6}2{44·610·79·85} topology. The different coordination modes of metal ions and dicarboxylates play important roles in the formation of final structures for title complexes.

Syntheses and Biological Activities of V-Shaped Symmetrical Triazolothiazine Oxadiazole Derivatives†

To build V-shaped symmetrical structure thiadiazole derivatives,isophthalic acid and 5-aminoisophthalic acid condensed with 3-aliphatic-1,2,4-triazole( 1) respectively. In POCl3 presence,fourteen symmetrical V-shaped triazolo-thiadiazole derivatives( 2a—2g and 3a—3g) were synthesized,wherein thirteen of them were first synthesized,and the structures of compounds 2 and 3 were characterized by infrared( IR),nuclear magnetic resonance( NMR) and high resolution mass spectrometer( HRMS). The inhibitory activities of the target compounds were screened for Cdc25 B and PTP1 B. The results showed that some compouds exhibited inhibitory activities against Cdc25 B,compounds 3b and 3f may be used as potential Cdc25 B inhibitors in the treatment of cancer. Compouds 3b—3g exhibited inhibitory activities against PTP1 B. Compounds 3b and 3e may be used as potential PTP1 B inhibitors in the treatment of diabetes.

Solid-state and solution characterization of half-sandwich Ru(II) complexes with carboxylic ligands containing N-based coordinating functions

The aminobenozic ligands 3-(4-aminophenyl)propionic acid (4APPA), 4-(4-aminophenyl)butyric acid (4APBA) and 5-aminoisophthalic acid (5AIPA) have been reacted with [(η6-p-cymene)RuCl2]2 giving rise to the corresponding half-sandwich Ru(II) complexes of formula [(η6-p-cymene)Ru(ligand)Cl2] (1, 2 and 3, respectively). The solid state structures of all three organometallic compounds have been elucidated by single crystal X-ray analysis conducted on crystals grown in MeOH or THF. The aminobenzoic ligands interact with the metal through the amine function, the pseudo-octahedral geometry being satisfied by a η6-coordinated p-cymene ring and by two chloride ligands. Dissolution of the complexes in coordinating solvents, such as dmso or acetonitrile led to ligand solvolysis, as evidenced by 1H NMR analysis. The lability of monodentate N-based ligands toward the organometallic fragment [(η6-p-cymene)RuCl2] was evidenced by the structural outcomes deriving from crystals grown in acetonitrile of the related compounds [(η6-p-cymene)Ru(INA)Cl2] (4) (INA = isonicotinic acid) and [(η6-p-cymene)Ru(4ABA)Cl2] (5) (4ABA = 4-aminobenzoic acid). These revealed, although in low yields, the occurred ligand solvolysis with formation of a cocrystal of formula {[(η6-p-cymene)Ru(INA)Cl2](H2O) (INA)} in the case of complex 4 and formation of the tetrakis–acetonitrile complex trans-[Ru(CH3CN)4Cl2] in the case of complex 5.

Supramolecular architecture of a 1:1 complex of 5-aminoisophthalic acid with 1,2-bis(4-pyridyl)ethane

The crystal structure has been solved for a 1:1 molecular complex of 5-aminoisophthalic acid and 1,2-bis(4-pyridyl)ethane. Crystal data: C20H19N3O4, M = 365.38, orthorhombic, P21/n space group; unit cell parameters: a = 10.7521(6) A, b = 11.9151(6) A, c = 13.7645(8) A, V = 1763.40(17) A3, Z = 4, dx = 1.376 g/cm3, R1 = 0.0514, T = 110 K. The 5-aminoisophthalic acid molecule is linked by O-H⋯N hydrogen bond to 1,2-bis(4-pyridyl)ethane, forming a linear hydrogen bonded chain running parallel to [0 3 0]. In the crystal, the intermolecular interactions link 5-aminoisophthalic acid molecules with head-tohead N-H⋯O hydrogen bonds generating R22(14) centrosymmetric dimers, which are extended head-totail via amine and carboxyl group N-H⋯O=C hydrogen bond. The supramolecular structure is consolidated by C-H⋯O hydrogen bonds and π⋯π interactions.

Theoretical study of the hydrogen bonding interaction between Levodopa and a new functionalized pillared coordination polymer designed as a carrier system

The solvothermal reaction of Co(NO3)2⋅6H2O, Pyrazine (L1) and 5-Aminoisophthalic acid (L2) let to the formation of a new functionalized pillared coordination polymer with possible application as a carrier system for drug delivery. The X-ray diffraction confirmed the structure of the material and theoretical density functional calculations using a non-empirical hybrid functional PBE0 were done to evaluate the possible hydrogen bonding interaction between the free amine group present in the pillared material and the carboxylic unit belonging to the pharmaceutical Levodopa. The stabilization energy for the model proposed resulted in 11kcal/mol.

Carbon Dioxide Capture and Dyes Separation in a Porous Framework with Anionic Sql Net

Presented here is a water-stable MOF material [ In (5- AIPA )2] ⋅ Me 2 NH 2(1; 5-AIPA = 5-Aminoisophthalic acid) built from the connecting of tetrahedral building units [ In ( COO )4]-. The sql net of compound 1 exhibits preferable chemical and thermal stability confirmed by thermal gravimetric analyses (TGA) and powder X-ray diffraction pattern (PXRD) measurements. The activated empty phase of 1a, as a good candidate material for CO 2 capture, shows a CO 2 uptake of 56.6 cm3/g and CH 4/ CO 2 selectivity in excess of 16.4. Remarkably, based on the cation exchange mechanism, 1a has excellent MB affinity and can adsorb MB over MO from water in two hours. The results further support the idea that the ionic MOFs can find more applications in the separation of ionic dyes for the purifying of dye wastewater.

Fluorous bis(oxazolines) ligand: Synthesis and application in Kabachnik-Fields reaction

A novel fluorous bis(oxazolines) ligand was synthesized with 70% overall yield in 5 steps starting from 5-aminoisophthalic acid. The ligand was applied in the one-pot synthesis of α-aminophosphonates via copper-catalyzed Kabachnik-Fields reaction, giving the corresponding products in moderate to excellent yields under mild conditions. Furthermore, the fluorous ligand could be easily recovered and reused for four times without significant loss of activity.

Chemical modification of MWCNTs with 5-aminoisophthalic acid and its effects on the thermal and morphological properties of chiral poly (ester-imide)/MWCNT nanocomposites having N-trimellitylimido-L-isoleucine moieties

In this article, carboxylated-multiwalled carbon nanotubes (MWCNT) s were functionalized with 5-aminoisophthalic acid under microwave irradiation conditions as a simple and efficient technique. Functionalized MWCNTs were incorporated into a chiral poly (ester-imide) (PEI) matrices using solution mixing and ultrasonic dispersion method. The optically active PEI was prepared by direct polycondensation reaction of chiral diacid with 4,4′-thiobis (2-tert-butyl-5-methylphenol) promoted by tosyl chloride in pyridine and N,N-dimethyl formamide solution. The nanocomposites (NC) s containing functionalized MWCNTs with loading levels of 5, 10, 15 wt.% were produced and studied in terms of morphology, thermal stability and chemical structure by X-ray diffraction, FT-IR spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy, and field emission scanning electron microscopy. It was found from TGA data that the NCs show improved thermal stability by comparison with the pure PEI as a result of uniform and efficient dispersion of functionalized MWCNTs in the PEI matrices. Microscopic observations indicated good filler dispersion and improved compatibility of the filler with polymer.

Syntheses, Characterization and Crystal Structures of Three New Copper(II) Complexes Based on N,N′-bis(4-pyridinecarboxamide)-1,4-butane and Three Different Aromatic Dicarboxylates

Three new copper(II) complexes based on the flexible N,N’-bis(4-pyridinecarboxamide)-1,4-butane (4-dpyb) and three different aromatic dicarboxylic acids [5-methylisophthalic acid (5-H2MIP), 5-aminoisophthalic acid (5-H2AIP), pyridine-2,6-dicarboxylic acid (2,6-H2PDA)], [Cu(4-dpyb)(5-MIP)(H2O)]·H2O (1), [Cu(4-dpyb)(5-HAIP)2] (2), [Cu(4-dpyb)0.5(2,6-PDA)]·H2O (3), have been hydrothermally synthesized. X-ray diffraction analysis reveals that complex 1 is a 2 D grid polymeric layer constructed by the [Cu-4-dpyb] chains and [Cu-5-MIP] chains, and the adjacent layers are further linked by hydrogen bonding interactions to form a 3 D supramolecular structure. Complex 2 is a 3 D supramolecular network based on the polymer chain [Cu(5-HAIP)2]n, in which the discrete 4-dpyb ligands are dispersed. Complex 3 represents a polymer chain based on the μ 4 -bridging 4-dpyb ligand, in which 2,6-PDA only serves as a terminal chelating ligand. For complex 3, the neighboring chains are extended into a 3 D supramolecular structure by hydrogen bonding and π–π stacking interactions. In these complexes, the flexible bis-pyridyl-bis-amide ligands 4-dpyb show the μ 2 -bridging mode (for 1), non-coordinated mode (for 2) and μ 4 -bridging mode (for 3), respectively, and three kinds of aromatic dicarboxylate anions (5-MIP, 5-HAIP and 2,6-PDA) also adopt three different coordination modes. The different coordination modes of ligands 4-dpyb and three dicarboxylates play important roles in the construction of final structures for title complexes. In addition, the thermal stabilities and fluorescent properties of complexes 1–3 have also been investigated. Three new 3 D supramolecular complexes based on 2 D polymer layers or 1 D chains, [Cu(4-dpyb)(5-MIP)(H2O)]·H2O (1), [Cu(4-dpyb)(5-HAIP)2] (2), [Cu(4-dpyb)0.5(2,6-PDA)]·H2O (3), have been hydrothermally synthesized. The different coordination modes of ligands 4-dpyb and three dicarboxylates play important roles in the construction of final structures for title complexes.