Benzophenone Dicarboxylic Acid Research Articles

Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization.

The in situ and systematic high-throughput investigation of the system Al3+/4,4'-benzophenonedicarboxylic acid (H2BPDC)/DMF/H2O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO6 polyhedra forming the inorganic building unit (IBU). These {Al8O8} IBUs are arranged in a bcu packing and connected via BPDC2- ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC2- linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO6 polyhedra connected by BPDC2- ions. Replacing H2BPDC by 4,4'-oxydibenzoic acid (H2ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)2(OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N2 and CO2, while the latter only adsorb CO2.

Metal-organic frameworks with 1,4-di(1H-imidazol-4-yl)benzene and varied carboxylate ligands for selectively sensing Fe(iii) ions and ketone molecules.

Four new metal-organic frameworks (MOFs) [Zn(L)(bpdc)]·1.6H2O (1), [Co(L)(bpdc)]·H2O (2), [Ni3(L)2(bptc)2(H2O)10]·2H2O (3) and [Cd2(L)(Hbptc)2] (4) were achieved by reactions of the corresponding metal salt with mixed organic ligands of 1,4-di(1H-imidazol-4-yl)benzene (L) and 4,4'-benzophenonedicarboxylic acid (H2bpdc) or biphenyl-2,4',5-tricarboxylic acid (H3bptc). They exhibit varied structures: MOFs 1 and 4 are porous three-dimensional (3D) frameworks, while 2 is an infinite one-dimensional (1D) chain and 3 is a two-dimensional (2D) network. Remarkably, 1 and 4 can act as potential fluorescent materials for sensing Fe(iii) ions and different ketone molecules with high selectivity and sensitivity. In addition, MOF 1 shows selective adsorption of CO2 over N2.

Hydrothermal Synthesis and Crystal Structure of a New Co(II) Coordination Polymer With One-Dimensional Helical Chains

A new Co(II) coordination polymer, [Co(bda)(bpa)]n (1) [H2bda = 4,4′- benzophenonedicarboxylic acid and bpa = bis(4-pyridyl)amiine], has been prepared by hydrothermal synthesis and characterized by IR, X-ray diffraction, and elemental analysis. Complex [Co(bda)(bpa)]n (1), triclinic system, space group P-1 with a = 12.015(5) Å, b = 13.195(5) Å, c = 16.922(5) Å, α = 104.801(5)°, β = 90.028(5)°, γ = 116.953(5)°, V = 2290.9(15) Å3, Z = 2, Mr = 498.35, Dc = 1.445 g/cm3, F(000) = 1020, and µ = 0.791 mm−1. The final refinement gave R = 0.0360and wR = 0.0450 for 8127 reflections with I > 2σ(I). X-ray diffraction analysis reveals that complex 1 shows a two-dimensional layer structure with one-dimensional helical chains.

Hydrothermal Synthesis and Crystal Structure of Ni(II) Coordination Polymer of 4,4'-Benzophenonedicarboxylic Acid and bis(4-pyridyl)amine

Hydrothermal Synthesis and Crystal Structure of Ni(II) Coordination Polymer of 4,4'-Benzophenonedicarboxylic Acid and bis(4-pyridyl)amine

First Keto-Functionalized Microporous Al-Based Metal–Organic Framework: [Al(OH)(O2C-C6H4-CO-C6H4-CO2)

Based on the V-shaped linker molecule 4,4'-benzophenonedicarboxylic acid, the new carbonyl-functionalized metal-organic framework (MOF) [Al(OH)(O(2)C-C(6)H(4)-CO-C(6)H(4)-CO(2))], denoted as CAU-8, was discovered employing high-throughput methods. The compound is obtained from 4,4'-benzophenonedicarboxylic acid, Al(2)(SO(4))(3)·18H(2)O in a mixture of N,N-dimethylformamide (DMF) and water under solvothermal conditions. The structure was determined from single-crystal X-ray diffraction data (I4(1)/a, a = b = 13.0625(5), c = 52.565(2) Å). The framework is based on infinite inorganic building units of trans-connected, corner-sharing AlO(6)-polyhedra. Parallel Al-O-chains are arranged in layers perpendicular to [001]. Within a layer an interchain distance of ∼1.1 nm is observed. The orientation of the Al-O-chains within neighboring layers is perpendicular to each other, along [100] and [010], respectively, and an ABCDA stacking of these layers is observed. The interconnection of these orthogonally oriented chains by the V-shaped dicarboxylate ions results in the formation a three-dimensional framework structure containing one-dimensional channels with a diameter of about 8 Å. The pore walls are lined by the keto-groups. CAU-8 was thoroughly characterized by X-ray powder diffraction (XRPD), thermogravimetric measurements, IR- and Raman-spectroscopy, elemental analysis, and gas sorption experiments using N(2) and H(2) as adsorptives. CAU-8 is stable up to 350 °C in air and exhibits a moderate porosity with a specific surface area of S(BET) = 600 m(2)/g and a micropore volume of 0.23 cm(3)/g. Moreover, a detailed topological analysis of the framework was carried out, and an approach for the topological analysis of MOFs based on infinite 1-periodic building units is proposed.

Effect of film thickness on the changes in gas permeability of a glassy polyarylate due to physical agingPart II. Mathematical model

Part I of this series documented a substantial loss in gas permeability over time for thin films of a glassy polyarylate made from bisphenol-A–benzophenone dicarboxylic acid. The rate of permeability loss, and, thus, aging was found to be dependent on film thickness in a way that suggested that physical aging occurs by two mechanisms. In this paper, a mathematical model was developed to quantitatively describe the physical aging process in terms of the free volume (permeability) loss observed using reasonable physical parameters. The model describes two simultaneous mechanisms of free volume loss: free volume diffusion to the film surface (thickness dependent) and lattice contraction (thickness independent). A step-wise model development is described with comparison to the data and optimization of the model parameters at each step. The final dual-mechanism model describes the experimental data presented in Part I remarkably well.

Effect of film thickness on the changes in gas permeability of a glassy polyarylate due to physical agingPart I. Experimental observations

The effects of thickness (0.25–33μm) and aging time on the gas permeation properties of films formed from a glassy polyarylate made from bisphenol-A benzophenone dicarboxylic acid were examined. Evidence is presented which shows that physical aging is responsible for a significant decrease in gas permeability with time following quenching the polymer from above its glass transition temperature; the rate of change is greater for the thinner films. Two methods of determining accurate film thicknesses were used to obtain absolute permeability coefficients. The importance of the permeation protocol on the aging rate was examined, and a reversal of the aging process was demonstrated by annealing the aged film above the Tg. These results indicate that physical aging occurs by two distinct simultaneous mechanisms: one which is thickness dependent and another that is not.

Wholly aromatic thermotropic liquid crystalline polyesters of 3,3?-bis(phenyl)-4,4?-biphenol with 4,4?-benzophenone dicarboxylic acid

A series of wholly aromatic, thermotropic polyesters, derived from 3,3′-bis(phenyl)-4,4′-biphenol (DPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various linear comonomers, were prepared by the melt polycondensation reaction and characterized for their thermotropic properties by a variety of experimental techniques. The homopolymer of DPBP with 4,4′-BDA had a fusion temperature (Tf) at 265°C, exhibited a nematic phase, and had a liquid crystalline range of 105°C. All of the copolyesters of DPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), or 50 mol % terephthalic acid (TA), 2,6-naphthalenedicarboxylic acid (2,6-NDA) had low Tf values in the range of 220–285°C, exhibited a nematic phase, and had accessible isotropization transitions (Ti) in the range of 270–420°C, respectively. Their accessible Ti values would enable one to observe a biphase structure. Each of the copolymers with HBA or HNA had a much broader range of liquid crystalline phase. In contrast, each of the copolymers with TA or 2,6-NDA had a relatively narrow range of liquid crystalline phase. Each of these polyesters had a glassy, nematic morphology that was confirmed with the DSC, PLM, WAXD, and SEM studies. As expected, they had higher glass transition temperatures (Tg) in the range of 161–217°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (Td) in the range of 494–517°C, respectively. Despite their noncrystallinity, they were not soluble in common organic solvents with the exception that the homopolymer and its copolymer with TA had limited solubility in CHCl3. However, they were soluble in the usual mixture of p-chlorophenol/1,1,2,2-tetrachloroethane (60/40 by weight) with the exception of the copolymer with 2,6-NDA. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 769–785, 1997

Fully aromatic thermotropic liquid crystalline polyesters of 3‐phenyl‐4,4′‐biphenol with 4,4′‐benzophenone dicarboxylic acid

AbstractA series of fully aromatic, thermotropic polyesters, derived from 3‐phenyl‐4,4′‐biphenol (MPBP), nonlinear 4,4′‐benzophenone dicarboxylic acid (4,4′‐BDA), and various other comonomers was prepared by the melt polycondensation method and characterized for their thermotropic liquid crystalline behavior by a variety of experimental techniques. The homopolymer of MPBP with 4,4′‐BDA had a fusion temperature (Tf) at 240°C, exhibited a nematic liquid crystalline phase, and had a narrow liquid crystalline range of 60°C. All of the copolyesters of MPBP with 4,4′‐BDA and either 30 mol % 4‐hydroxybenzoic acid (HBA), 6‐hydroxy‐2‐naphthoic acid (HNA) or 50 mol % terephthalic acid (TA), 2,6‐naphthale‐nedicarboxylic acid (2,6‐NDA) and low Tf values in the range of 210–230°C, exhibited a nematic phase, and had accessible isotropization transitions (Ti) in the range of 320–420°C, respectively. As expected, each of them had a broader range of liquid crystalline phase than the homopolymer. They had a “frozen” nematic, glassy order as determined with the wide‐angle X‐ray diffraction (WAXD) studies. The morphology of each of the “as‐made” polyesters had a fibrous structure as determined with the scanning electron microscopy (SEM), which arises because of the liquid crystalline domains. Moreover, they had higher glass transition temperatures (Tg) in the range of 167–190°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (Td) in the range of 500–533°C, respectively. © 1995 John Wiley & Sons, Inc.

Wholly aromatic thermotropic liquid crystalline polyesters of 4,4′‐biphenol, substituted biphenols, and 1,1′‐binaphthyl‐4,4′‐diol with 3,4′‐benzophenone dicarboxylic acid

AbstractWholly aromatic, thermotropic homopolyesters, derived from 4,4′‐biphenol, substituted biphenols, or 1,1′‐binaphthyl‐4,4′‐diol and 3,4′‐benzophenone dicarboxylic acid, and two copolyesters, each of which contained 30 mol % of 6‐hydroxy‐2‐naphthoic acid, were prepared by acidolysis polycondensation reactions and characterized for their liquid crystalline properties. The solubility behavior of these polymers has also been investigated. The two homopolymers of phenyl‐substituted biphenols with 3,4′‐benzophenone dicarboxylic acid were soluble in many common organic solvents. All of the homopolymers had lower Tm/Tf values than those with terephthalic acid, which was attributed to the incorporation of the asymmetric 3,4′‐benzophenone dicarboxylate units in a head‐to‐head and head‐to‐tail fashion along the polyester chain. Two copolymers had lower Tm values than those of the respective homopolymers, as expected. They formed nematic phases which persisted up to 400°C, except those of phenyl‐substituted biphenols with 3,4′‐benzophenone dicarboxylic acid. Each of these two polymers also exhibited an accessible Ti transition, and had a broad range of LC phase. They had glass transition temperatures, Tg, in the range of 139‐209°C and high thermal stabilities in the temperature range of 465‐511°C. © 1995 John Wiley & Sons, Inc.

Fully aromatic thermotropic liquid crystalline homopolyesters of 3,4′‐benzophenone dicarboxylic acid

AbstractA series of fully aromatic, thermotropic homopolyesters, derived from 3,4′‐benzophenone dicarboxylic acid and various aromatic diols, was prepared by the melt polycondensation method and examined for thermotropic behavior by a variety of experimental techniques. The aromatic diols used in the study were hydroquinone, 2,6‐, 1,4‐, 1,5‐, 2,3‐, and 2,7‐naphthalenediol isomers. All of the homopolyesters of 3,4′‐benzophenone dicarboxylic acid with aromatic diols (except that with 2,7‐naphthalenediol) formed a nematic LC phase in the melt. They had the glass transition temperatures (Tg) in the range of 133–164°C, the melting transitions (Tm) in the range 305–360°C and the high thermal stabilities (Td) in the range of 410–483°C. The 2,6‐naphthalenediol based homopolymer had the highest Tm (360°C) and the 2,3‐naphthalenediol based homopolymer had the lowest Tm (305°C) among all of the homopolymers of naphthalenediol isomers. © 1994 John Wiley & Sons, Inc.

Benzophenone dicarboxylic acid antagonists of leukotriene B4. 1. Structure-activity relationships of the benzophenone nucleus

A series of lipophilic benzophenone dicarboxylic acid derivatives was prepared which inhibited the binding of the potent chemotaxin leukotriene B4 to its receptor(s) on intact human neutrophils. With a radioligand-binding assay as a measure of receptor affinity, a structure-activity relationship for this series was investigated. Both acidic residues were required for receptor-binding activity. The relative orientation of the two acidic groups was important for optimal binding. Replacement of the carbonyl group of the benzophenone with a variety of polar and nonpolar linking groups led to only small changes in binding affinity, indicating the linking group may not be involved in receptor recognition. Further structure-activity relationships within this series are reported in an accompanying paper.

Benzophenone dicarboxylic acid antagonists of leukotriene B4. 2. Structure-activity relationships of the lipophilic side chain

A series of lipophilic benzophenone dicarboxylic acid derivatives were found to inhibit the binding of the potent chemotaxin leukotriene B4 (LTB4) to its receptor on intact human neutrophils. Activity at the LTB4 receptor was determined by using a [3H]LTB4-binding assay. The structure-activity relationship for the lipophilic side chain was systematically investigated. Compounds with n-alkyl side chains of varying lengths were prepared and tested. Best inhibition of [3H]LTB4 binding was observed with the n-decyl derivative. Analogues with alkyl chains terminated with an aromatic ring showed improved activity. The 6-phenylhexyl side chain was optimal. Substitution on the terminal aromatic ring was also evaluated. Methoxyl, methylsulfinyl, and methyl substituents greatly enhanced the activity of the compound. For a given substituent, the para isomer had the best activity. Thus the nature of the lipophilic side chain can greatly influence the ability of the compounds to inhibit the binding of LTB4 to its receptor on intact human neutrophils. The most active compound from this series, 84 (LY223982), bound to the LTB4 receptor with an affinity approaching that of the agonist.

Phosphorescence and photochemical studies of some benzophenone dicarboxylic acid esters

Phosphorescence quantum yields and lifetimes in solution in carbon tetrachloride were measured for dimethyl esters of three benzophenone dicarboxylic acids. Curious features were noted. The triplet energies (in kilocalories per mole) varied with substitution ((3,3), 67.0; (3,4), 65.6; (4,4), 64.8), as did the phosphorescence lifetimes (14 μs, 26 μs and 45 μs respectively). The radiative rate constants k p = 165 ± 10 s −1 were identical. The triplets of all three ketones reacted with n-octane with a second-order rate constant of 1.14 × 10 6 M −1s −1 at 22 °C.