Organic Amine Molecules Research Articles

Molecular design and experimental study on the alkylation of benzene with C6 olefin dimer with Lewis acidic monoamine ionic liquids and its sulfonate surfactant properties

Long-chain alkyl benzene (LAB), conventionally manufactured by petrochemical routes, is an important intermediate for the synthesis of high-value chemicals, especially detergents and oil displacement agents. The preparation of LAB from coal-based olefins has attracted extensive research interest. In this work, the alkylation activity of four Lewis acidic monoamine chloroaluminate ionic liquids (LAMCILs), designed by AlCl3 and monoamine hydrochloride with alkyl chains of different lengths, was predicted by quantum chemical calculations using the synthesis of 1-methyl-1-butylheptylbenzene (MBHB) with benzene and C6 olefin dimer as a model reaction. The HOMO*-LUMO* gap indicated that the alkylation activity was enhanced with increasing alkyl chain length of the organic amine molecules in the LAMCILs, in the following order: [n-C6H13NH3]Cl-AlCl3 > [n-C4H9NH3]Cl-AlCl3 > [n-C3H7NH3]Cl-AlCl3 > [C2H5NH3]Cl-AlCl3. These four LAMCILs were successfully synthesized and used to catalyze the alkylation of benzene with the C6 olefin dimer. The experimental results are consistent with the calculated results. The UV/VIS characterization showed that their Hammett acidity function (H0) increased as the alkyl chain of organic monoamine molecules in the LAMCILs extended. Therefore, a two-way correlation between the HOMO*-LUMO* gap, MBHB yield and Hammett acidity function can be established. Furthermore, the effect on the yield of MBHB was investigated by the method of metal chloride modified [n-C4H9NH3]Cl-AlCl3 ionic liquids. The results showed that the CuCl2-modified [n-C4H9NH3]Cl-AlCl3 ionic liquid had better catalytic activity in this study. Under optimal reaction conditions, the conversion of the C6 olefin dimer and selectivity toward MBHB reached 100 % and 91.34 %, respectively. Finally, the surfactant properties of sodium 1-methyl-1-butylheptylbenzene sulfonate (SMBHBS) were examined, and the results indicated that its surfactant properties were basically comparable to those of commercial LAS.

Synthesis and properties of a novel photochromic metal organic framework for rapid amine selective sensing and Cr2O72− detection

A new photochromic metal organic frameworks (MOFs) have been synthesized by using a viologen ligand, named 1,1′-bis(3,5-carboxylatobenzyl)-(4,4′-bipyridinium) dichloride (H4bdcbpy•2Cl) and Cd(NO3)2·4H2O. This MOF (Cd-bdcbpy) features a three-dimensional (3D) framework structure, exhibiting photochromic properties under the irradiation of white light, blue light, UV light and heat with obvious color change from light yellow to dark green. Meanwhile, Cd-bdcbpy displays a visible color change to the naked eye when exposed to different organic amine molecules (ammonia, aniline, o-methylaniline and diphenylamine). Moreover, the detection of ammonia has been confirmed by the visual color changing phenomenon and luminescence quenching experiment and it can detect ammonia in very low concentrations (10-6 ​M). Attractively, through luminescence quenching, Cd-bdcbpy can be used as a multi response sensor for Cr2O72− anion in aqueous solution.

Aminosilanes grafted nanocrystalline cellulose from oil palm empty fruit bunch aerogel for carbon dioxide capture

The modification of solid adsorbents with aminating agents amid severe climate change has been intensively studied. Previous organic carbon dioxide (CO 2 ) sorbent like nanoporous activated carbon develops micropores but can be easily blocked by organic amine molecules during the impregnation process. Therefore, in this study, aminosilanes with different chain lengths and nitrogen (N) content were used in nanocrystalline cellulose (NCC) modification prior to solid adsorbent aerogel fabrication to investigate their effect on pore formation, surface area, thermal stability, and capacity of CO 2 capture. The NCC derived from oil palm empty fruit bunch fiber (OPEFB) has been modified with 3-(aminopropyl) trimethoxysilane (APTMS), 3-(2-aminoethylamino) propyl-dimethoxymethylsilane (AEAPDMS), and N-(3-trimethoxysilylpropyl) diethylenetriamine (DET3) by grafting method, respectively. Based on the results, aerogel modified with the shortest chain length aminosilane, APTMS-NCC aerogel has a higher CO 2 sorption (0.20 mmol/g adsorbent) than the unmodified NCC aerogel (0.10 mmol/g adsorbent). Meanwhile, the highest surface area properties and thermal stability are demonstrated by NCC grafted by the intermediate chain length aminosilane, AEAPDMS-NCC aerogel. Thus, our work concluded that NCC's modification with low and intermediate chain length and N content aminosilanes prior to aerogel fabrication improved the pore formation, surface area, and CO 2 sorption of the aerogel. The aerogels from aminosilanes functionalized NCC could be developed as a new value-added product in the palm oil industry.

Reticulation of 2D Semiconductors by Metal–Organic Approach for Efficient Hydrogen Evolution

We report a universal approach to synthesize a series of three-dimensional (3D) metal–organic constructs by linking 2D metal dichalcogenides with organic amine molecules [p-phenylenediamine (PPDA),...

Luminescent Cu(I)-I Coordination Compound for Detection of Organic Amines Both in Liquid and Vapor Phase

Detection of trace amounts of organic amines is significantly important for public security and environment protection. One luminescence functional Cu(I)-I coordination compound, Cu2I2(3-pc)4 (1) (3-pc = 3-picoline) was selected for detecting of organic amines by electron transfer between 1 and organic amine molecules. Detailed investigation of the luminescence properties of 1 revealed that it can sense a family of organic amines both in liquid and vapor phase at room temperature. The fluorescent experiments show that 1 can detect a family of organic amines solution by fluorescent quenching with different degree. Meanwhile, the visual colors of 1 changed when exposed to different amines vapors. The detection limits of all organic amines could reach about 10−5 mol L−1.

In situ photochemical synthesis noble-metal-free NiS on CdS-diethylenetriamine nanosheets for boosting photocatalytic H2 production activity

Cadmium sulfide (CdS), as a promising semiconductor photocatalyst, has been widely investigated in the hydrogen (H2) evaluation field from splitting water, in order to settle environmental problems and energy shortages. But serious photocorrosion and low visible light absorption limited its H2 production performance. In our work, we first synthesized inorganic-organic CdS-diethylenetriamine (CdS-DETA) nanosheets via microwave hydrothermal method. The small organic amine molecules will link normal CdS nanoparticles together to form nanosheets with large surface area, which can reduce overpotential of H2 evolution reaction and promoted the separation of photo-induced carriers. Then, the nickel sulfide (NiS) was deposited on the surface of CdS-DETA by a fast and simple photochemical method, demonstrating that the H2 production performance was further improved. Specifically, the best H2 production rate of NiS/CdS-DETA composite is up to 230.6 μmol·h−1 under visible light, which is 8.42 and 1.72 times as high as that of pure CdS nanoparticles and CdS-DETA hybrid, and even stronger than that of Pt/CdS-DETA (173.8 μmol·h−1). Moreover, the photocatalytic H2 evolution rate is still stable after 16 h of cycle testing. Besides, the photocatalytic mechanism using NiS as a cocatalyst has also been proposed, where NiS can effectively accelerate the separation of photoinduced holes and electrons for CdS-DETA. This work embodied a feasible method to design photocatalysts to convert sun light into clean H2 energy more efficiently and stably.

A novel photochromic coordination polymer based on a robust viologen ligand exhibiting multiple detection properties in the solid state.

A new photochromic and porous Cd(ii) coordination polymer (CP) has been synthesized by using a robust viologen ligand, named 1-(3-carboxybenzyl)-4,4'-bipyridinium chloride (m-Hbcbpy·Cl) and CdCl2·2H2O. This CP (Cd-bcbpy) shows a fast response and reversible photochromism through the progress of ET due to the formation of viologen radicals. Cd-bcbpy shows a sharp response to blue rays and selectively detects organic amine molecules, which are electron rich, in the solid state due to the electron-deficient properties of m-Hbcbpy·Cl. The detection of organic amine and benzene molecules has been confirmed by the visual color changing phenomenon and luminescence quenching experiment. Cd-bcbpy can detect aniline in very low concentrations (10-4 M). In addition, the structure of Cd-bcbpy maintains stability in aqueous solutions of hydrochloric acid with the pH ranging from 1 to 7. The photo-controlled luminescence properties of this CP, during the coloration-decoloration process, have been studied.

Achieving efficient room-temperature catalytic H2 evolution from formic acid through atomically controlling the chemical environment of bimetallic nanoparticles immobilized by isoreticular amine-functionalized metal-organic frameworks

From the viewpoint of controlling the catalytic performance of supported metal nanoparticles (NPs) through tuning their chemical environment in the atom level, we have used electron-donating amino groups and three organic amine molecules to modify the organic linkers and unsaturated coordination Cr3+ sites in one porous metal-organic framework MIL-101 with atomically precise structures, respectively, and then we have prepared a series of AuPd NPs immobilized by the two types of functional MIL-101 supports. The as-synthesized AuPd NPs were used for the catalytic dehydrogenation of formic acid (HCOOH) and the results showed that these catalysts exhibited remarkably different activities and H2 selectivities at 298K. Particularly, the AuPd NPs immobilized by MIL-101-NH2 presented 100% of H2 selectivity and the highest activity because of the synergistic steric and electronic effects, which were related to the activation of HCOOH and enrichment of electron density of active Pd species. The investigation of UV–vis spectroscopy showed that the reaction between the mixed metal ions (AuCl4− and PdCl42−) and the four functional MIL-101 supports generated four different coordination complex intermediates, which played an important role in yielding AuPd NPs with different chemical environment and inducing different catalytic performance.

Novel amine templated three-dimensional zinc-organophosphonates with variable pore-openings

Amine templated three-dimensional zinc-organophosphates with different ring sizes have been obtained by varying the organic amine molecules. The figure shows the various net structures obtained during the study.

Multicomponent hydrogen-bonding organic solids constructed from 6-hydroxy-2-naphthoic acid and N-heterocycles: Synthesis, structural characterization and synthon discussion

Seven novel multicomponent crystals involving various substituted organic amine molecules and 6-hydroxy-2-naphthoic acid were prepared and characterized by using single crystal X-ray diffraction, infrared and thermogravimetric analyses (TGA). Crystal structures with 1,4-bis(imidazol) butane (L1) 1, 1,4-bis(imidazol-1-ylmethyl)benzene (L2) 2, 1-phenyl piperazine 3, 2-amino-4-hydroxy-6-methyl pyrimidine 4, 4,4'-bipyridine 5, 5,5'-dimethyl-2,2'-dipyridine 6, 2-amino-4,6-dimethyl pyrimidine 7 were determined. Among the seven molecular complexes, total proton transfer from 6-hydroxy-2-naphthoic acid to coformer has occurred in crystals 1–4, while the remaining were cocrystals. X-ray single-crystal structures of these complexes reveal that strong hydrogen bonding O–H···O/N–H···O/O–H···N and weak C–H···O/C–H···π/π···π intermolecular interactions direct the packing modes of molecular crystals together. The analysis of supramolecular synthons in the present structures shows that some classical supramolecular synthons like pyridine-carboxylic acid heterosynthon R22(7) and aminopyridine-carboxylic acid heterosynthon R22(8), are again observed in constructing the hydrogen-bonding networks in this paper. Besides, we noticed that water molecules act as a significant hydrogen-bonding connector in constructing supramolecular architectures of 3, 4, 6, and 7.

Four calcium(ii) coordination polymers based on 2,5-dibromoterephthalic acid and different N-donor organic species: syntheses, structures, topologies, and luminescence properties

By using different N-donor organic species as additional auxiliary ligands with structure-directing roles, four three-dimensional (3D) calcium-based coordination complexes, [Ca(dbt)(H2O)]n1, [Ca(H-dbt)2(5,5′-dmbpy)2]n2, (4,4′-bpy)0.5[Ca(dbt)(H2O)2]n3, and (H2-dib)[Ca3(dbt)4(H2O)4·2H2O]n4 (H2-dbt = 2,5-dibromoterephthalic acid, 2,2′-bpy = 2,2′-bipyridine, 5,5′-dmbpy = 5,5′-dimethyl-2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine, dib = 1,4-di(1H-imidazol-1-yl)benzene), have been successfully synthesized under similar solvothermal conditions and structurally characterized. The organic amine molecules play different roles in the formation of four different metal–organic skeletons with diverse structural topologies, in which complexes 1–3 are neutral, and 4 comprises a negatively charged framework with diprotonated dib as the counterion. Complex 1 features a 3D (6,6)-connected framework structure composed of edge-sharing 1D Ca–O–Ca inorganic chains and dbt ligands. The 2,2′-bpy molecule plays an important role in the synthesis of 1 as the structure-directing agent (SDA). Complex 2 shows a 3D 2-fold interpenetrated diamondoid framework (dia, 66) formed by single metal nodes via linear H-dbt anions and bidentate chelating 5,5′-dmbpy ligands, while complex 3 exhibits a 3D noninterpenetrated pcu network with {412·63} topology constructed from binuclear [Ca2(CO2)4] secondary building units and two types of dbt ligands, in which 4,4′-bpy molecules are ordered within the 3D neutral calcium-based framework as template and space filling agents. Complex 4 is a unique (4,4,4,4,5)-connected 5-nodal topology net, in which the diprotonated dib molecules provide space filling to balance the negatively charged framework. In addition, the thermal stability and the fluorescence properties of complexes 1–4 have been investigated.

Crystal Chemistry of Uranyl Carboxylate Coordination Networks Obtained in the Presence of Organic Amine Molecules

AbstractThree uranyl isophthalates (1,3‐bdc) and two uranyl pyromellitates (btec) of coordination‐polymer type were hydrothermally synthesized (200 °C for 24 h) in the presence of different amine‐based molecules [1,3‐diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N‐dimethylformamide]. (UO2)2(OH)2(H2O)(1,3‐bdc)·H2O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H2O molecules. The compounds (UO2)1.5(H2O)(1,3‐bdc)2·0.5H2dap·1.5H2O (2) and UO2(1,3‐bdc)1.5·0.5H2dap·2H2O (3) consist of discrete uranyl‐centered hexagonal bipyramids connected to each other by a ditopic linker to form a single‐layer network for 2 or a double‐layer network for 3. The protonated diamine molecules are located between the uranyl–organic sheets and balance the negative charge of the layered sub‐networks. The phase (UO2)2O(btec)·2Hdma·H2O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO2(btec)·2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non‐bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen‐bond network. The different illustrations show the structural diversity of uranyl–organic coordination polymers with organic amine molecules as countercations.

Synthesis, characterization, and properties of the first indium borogermanate incorporating an organic amine ligand: InBGe2O6(OH)2(CH3CH(NH2)CH2NH2)·2H2O

A new indium borogermanate incorporating an organic amine ligand, InBGe2O6(OH)2(CH3CH(NH2)CH2NH2)·2H2O, was synthesized under solvothermal conditions and characterized by infrared spectroscopy, thermogravimetric analysis, and emission spectroscopy. This compound is a new example of the combination of metal, boron, and germanium atoms into one structure in the presence of organic amine molecules. Its 2D sheets with one 3-, one 4-, and two types of 6-membered rings consist of In2O6N4 octahedral dimers, Ge2O6(OH) double tetrahedra, and BO3(OH) groups that are interconnected by water molecules to form a 3D supramolecular framework. Interestingly, the emission spectrum for this compound displays a strong broad band centered at 455nm.

Growth of Fe3O4 nanoparticles with tunable sizes and morphologies using organic amine

Fe3O4 nanoparticles (NPs) have been synthesized by the thermal decomposition of iron oleate complex in 1-octadecene solutions using organic amines as stabilizers such as trioctylamine (TOA), oleylamine (OAm), and hexadecylamine (HDA). By optimizing preparation conditions such as temperature, time, and the concentration of reaction reagents, the NPs exhibited adjusted sizes and morphologies (spherical, truncated octahedral, cubic, and tetrahedral). Organic amines play an important role for the morphology of the NPs. For example, truncated octahedral shape was gradually changed into quasi-cubic shape if adding TOA in the reaction system for a long time. In contrast, spherical, cubic, and tetrahedral Fe3O4 NPs were fabricated in the case of OAm used. Because of OAm used as a reducing agent, reaction temperature was decreased. HDA resulted in spherical Fe3O4 NPs a large size. It is confirmed that organic amine molecules were bound on the surface of the NPs by measuring the Fourier transformation infrared spectroscopy of samples.

The role of small organic amine molecules and their aggregates in the crystallization of microporous materials

A series of 1,6-hexamethylenediamine (1,6-HDA) solutions with different concentrations were prepared and used as the structure directing agents for the crystallization of microporous materials. The surface tension of these solutions has been measured to inspect the assembly behavior of 1,6-HDA molecules. It has been found that the surface tension of these solutions decrease with the increase of 1,6-HDA concentration, which is similar to what in surfactant CTAB (Cetyl trimethyl ammonium bromide) solutions. When they were used to direct the crystallization of aluminophosphites, zincophosphates, and aluminophosphates, it was found that at low concentration, 1,6-HDA molecules cannot affect the crystallization process, and three-dimensional frameworks without 1,6-HDA in it were obtained. When 1,6-HDA concentration increased, the surface tension of these solution decreased sharply, and 1,6-HDA containing three-dimensional (3-D) frameworks were formed. 1,6-HDA molecules retained in these structure were not in assembling state, but in independent state. At high 1,6-HDA concentration, the surface tension of the solutions changed slowly accompanying with the assembly of 1,6-HDA molecules. It always resulted in the formation of layered structures with the inorganic layers interleaved by composite layers of diprotonated 1,6-HDA. Formation of large-micropore containing 3-D frameworks mainly resulted from the interaction between inorganic framework and organic amine at proper ratio, not from the assembly of 1,6-HDA molecules. Otherwise, the aggregates of 1,6-HDA molecules favors the formation of layered materials.

Effect of Single-Walled Carbon Nanotube Association upon 1H NMR Spectra of Amines

In order to quantify and study the complexation of small organic amine molecules with SWCNTs, the effect of SWCNT association upon their proton NMR spectra was studied. Results reveal that (1) a greater magnitude of chemical shift change for α protons to the amino group upon SWCNT association suggests close proximity of the amine nitrogen to SWCNTs except for the pyridines, (2) tertiary amines associate strongly with SWCNTs due to the inductive effect outweighing the steric effect of their alkyl parts, (3) in secondary amines, the steric effect overpowers the inductive effect resulting in their weaker interaction than tertiary amines with SWCNTs, (4) introduction of an alkyl substituent at the α position in primary amines results in more effective SWCNT association than at the amino nitrogen in secondary amines, (5) aromatic amines associate more strongly than aliphatic ones due to availability of more points of association, and (6) pyridines seem to interact via their π-electron cloud.

Intercalation of organic molecules into SnS2 single crystals

SnS2 is a layered semiconductor with a van der Waals gap separating the covalently bonded layers. In this study, post-synthesis intercalation of donor organic amine molecules, such as ethylenediamine (en), into tin disulfide and secondary intercalation of p-phenylenediamine (PPD) and 1, 5-naphthalenediamine (NDA) into SnS2_en have been verified with X-ray diffraction. PPD and NDA did not intercalate directly even during prolonged annealing but replaced en readily if en was already present in the van der Waals gap. The c-lattice dilation is proportional to the intercalant size. Unit cell lattices of intercalated products were determined from the positions of the X-ray diffraction peaks. Optical images taken during the intercalation showed that intercalation progressed from the periphery towards the interior of the crystal. TEM diffraction patterns in the [001] direction of SnS2 after intercalation revealed defects and stacking mismatches among the SnS2 layers caused by the intercalation. UV–Vis absorption studies showed a red shift in the band edge of the SnS2 material after intercalation. The band edge was 2.2eV for pristine SnS2; after intercalation with en or PPD, the absorbance spectra band edges shifted to approximately 0.7eV or 0.5eV, respectively.

Mechanistic study on the synthesis of one-dimensional yttrium aluminum garnet nanostructures under supercritical hydrothermal conditions in the presence of organic amines

Novel one-dimensional nanostructures of yttrium aluminum garnet were synthesized under supercritical hydrothermal conditions in the presence of organic amine molecules. In addition, the effect of different reaction parameters such as the presence of organic amine molecules, pH of the precursor solution, and the state of water (sub- or supercritical conditions) on the morphology of the final product was investigated. In this paper, considering the simultaneous effects of these different parameters, a new electrostatic model is proposed to explain the formation mechanism of the obtained nanostructures.

Review. Synthesis of Inorganic-Organic Hybrid Thiometallate Materials with a Special Focus on Thioantimonates and Thiostannates and in situ X-Ray Scattering Studies of their Formation

A rich variety of inorganic-organic hybrid thioantimonates and thiostannates were prepared during the last few years under solvothermal conditions applying organic amine molecules or transition metal complexes as structure directors. In this review synthetic approaches to and structural features of these thiometallates are discussed. For thioantimonates(III) the structures range from well isolated thioanions to three-dimensional networks, whereas the structural chemistry of thiostannates(IV) is strongly dominated by the [Sn2S6]4− anion, and no three-dimensional thiostannate has been reported so far. In the structures of thioantimonates(III) several primary building units like the [SbS3] trigonal pyramid, the [SbS4] unit or even the [SbS5] moiety are joined by vertex- and/or edge-linkages to form building blocks of higher structural hierarchy like [Sb3S4] semi-cubes or SbxSx heterocycles. A pronounced difference between thioantimonate and thiostannate chemistry is the tendency of Sb(III) to enhance the coordination geometry via so-called secondary bonds. In most cases the environment of Sb(III) is better described as a 3+n polyhedron with n = 1 - 3. The thioantimonate(V) structural chemistry is less rich than that of thioantimonates(III), and the [SbS4]3− anion shows no tendency for further condensation. By applying suitable multidentate amine molecules, transition metal cations which normally prefer bonding to the N atoms of the amines can be incorporated into the thiometallate frameworks

Amine-Templated Aluminoborates Exhibiting Graphite and Diamond Nets

A solvothermal reaction of Al2O3, H3BO3, pyridine, and H2O at 180 °C/7 days in the presence of organic amine molecules gave rise to four new aluminoborates, [(C6H18N2)(AlB6O13H3)], I; [(C5H16N2)(AlB5O10)]·2H2O, II; [(C5H16N2)(AlB5O10)], III; and [(C5H17N3)(AlB5O10)]·H2O, IV, with two- and three-dimensional structures. All the structures have been formed by the connectivity involving Al3+ ions and [B5O10] cyclic pentaborate units. In I, the 3-connected trigonal nodes form a layer that resembles a graphite structure has been observed. The compounds II, III, and IV, have 4-connected nodes that forms a diamond related three-dimensional structure. The formation of solvatomorphs in II and III is noteworthy and has been observed first time in a family of amine templated aluminoborates. A comparison of the various aluminoborate structures reveals subtle relationships between the organic amines (length of the amines) and the final framework structures. The compounds have been characterized using a variety of techniques including IR, second-order optical behavior, and MAS NMR studies.