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1.
Molecules ; 25(11)2020 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-32485968

RESUMO

New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N'-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications.

2.
J Org Chem ; 85(9): 5884-5894, 2020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32174116

RESUMO

Cethyl-2-methylresorcinarene (A), pyridine (B), and a set of 10 carboxylic acids (Cn) associate to form A·B·Cn ternary assemblies with 1:1:1 stoichiometry, representing a useful class of ternary systems where the guest mediates complex formation between the host and a third component. Although individually weak in solution, the combined strength of the multiple noncovalent interactions organizes the complexes even in a highly hydrogen-bond competing methanol solution, as explored by both experimental and computational methods. The interactions between A·B and Cn are dependent on the pKa values of carboxylic acids. The weak interactions between A and C further reinforce the interactions between A and B, demonstrating positive cooperativity. Our results reveal that the two-component system such as that formed by A and B can form the basis for the development of specific sensors for the molecular recognition of carboxylic acids.

3.
ACS Omega ; 4(16): 16891-16898, 2019 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-31646235

RESUMO

Three-dimensionally printed solid but highly porous polyamide-12 (PA12) plate-like filters were used as selective adsorbents for capturing tetrachloroaurate from acidic solutions and leachates to prepare PA12-Au composite catalysts. The polyamide-adsorbed tetrachloroaurate can be readily reduced to gold nanoparticles by using sodium borohydride, ascorbic acid, hydrogen peroxide, UV light, or by heating. All reduction methods led to polyamide-anchored nanoparticles with an even size distribution and high dispersion. The particle sizes were somewhat dependent on the reduction method, but the average diameters were typically about 20 nm. Particle sizes were determined by using a combination of single-particle inductively coupled plasma mass spectrometry, helium ion microscopy, and powder X-ray diffraction. Dispersion of the particles was analyzed by scanning electron microscopy with energy-dispersive spectroscopy. Due to the high adsorption selectivity of polyamide-12 toward tetrachloroaurate, the three-dimensional-printed filters were first used as selective gold scavengers for the acidic leachate of electronicwaste (WEEE). The supported nanoparticles were then generated directly on the filter via a simple reduction step. These objects were used as catalysts for the reduction of 4-nitrophenol to 4-aminophenol. The described method provides a direct route from waste to catalysts. The selective laser sintering method can be used to customize the flow properties of the catalytically active filter object, which allows the optimization of the porous catalytic object to meet the requirements of catalytic processes.

4.
J Am Chem Soc ; 141(40): 16033-16045, 2019 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-31532209

RESUMO

The study of the structures and properties of atomically precise gold nanoclusters is the object of active research worldwide. Recently, research has been also focusing on the doping of metal nanoclusters through introduction of noble metals, such as platinum, and less noble metals, such as cadmium and mercury. Previous studies, which relied extensively on the use of mass spectrometry and single-crystal X-ray crystallography, led to the assignment of the location of each of these foreign-metal atoms. Our study provides new insights into this topic and, particularly, compelling evidence about the actual position of the selected metal atoms M = Pt, Pd, Hg, and Cd in the structure of Au24M(SR)180. To make sure that the results were not dependent on the thiolate, for SR we used both butanethiolate and phenylethanethiolate. The clusters were prepared according to different literature procedures that were supposed to lead to different doping positions. Use of NMR spectroscopy and isotope effects, with the support of mass spectrometry, electrochemistry, and single-crystal X-ray crystallography, led us to confirm that noble metals indeed dope the cluster at its central position, whereas no matter how the doping reaction is conducted and the nature of the ligand, the position of both Cd and Hg is always on the icosahedron shell, rather than at the central or staple position, as often reported. Our results not only provide a reassessment of previous conclusions, but also highlight the importance of NMR spectroscopy studies and cast doubts on drawing conclusions mostly based on single-crystal X-ray crystallography.

5.
Inorg Chem ; 58(8): 5265-5272, 2019 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-30938518

RESUMO

Fe(III) porphyrins bridged with 1,2,3-triazole ligands were synthesized. Upon deprotonation, the triazolate ion coordinates to the Fe(III) ion, forming an overall neutral high-spin Fe(III) porphyrin in which the triazolate serves both as an axial ligand and as the counterion. The second axial coordination site is activated for coordination and binds p-methoxypyridine, forming a six-coordinate low-spin complex. Upon addition of a phenylazopyridine as a photodissociable ligand, the spin state of the complex can be reversibly switched with ultraviolet and visible light. The system provides the basis for the development of switchable catalase- and peroxidase-type catalysts and molecular spin switches.

6.
Chempluschem ; 84(2): 222-225, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31950695

RESUMO

Metal-organic frameworks (MOFs) have raised a lot of interest, especially as adsorbing materials, because of their unique and well-defined pore structures. One of the main challenges in the utilization of MOFs is their crystalline and powdery nature, which makes their use inconvenient in practice. Three-dimensional printing has been suggested as a potential solution to overcome this problem. We used selective laser sintering (SLS) to print highly porous flow-through filters containing the MOF copper(II) benzene-1,3,5-tricarboxylate (HKUST-1). These filters were printed simply by mixing HKUST-1 with an easily printable nylon-12 polymer matrix. By using the SLS, powdery particles were fused together in such a way that the structure of the printed solid material resembles the structure of a powder bed. The MOF additive is firmly attached only on the surface of partially fused polymer particles and therefore remains accessible to fluids passing through the filter. Powder X-ray analysis of the printed object confirmed that printing did not have any negative impact on the structure of the MOF. CO2 -adsorption studies also showed that the activity of the MOF was not affected by the printing process. SLS offers a straightforward and easy way to fabricate tailor-made MOF-containing filters for practical applications.

7.
Inorg Chem ; 57(21): 13901-13911, 2018 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-30351085

RESUMO

Condensation of persilylated nicotinimideamide and isonicotinimideamide with sulfur monochloride affords double salts of the 3-, 4-pyridyl-substituted 1,2,3,5-dithiadiazolylium DTDA cations of the general formula [3-, 4-pyDTDA][Cl][HCl] in which the pyridyl nitrogen serves as a noninnocent base. Reduction of these salts with triphenylantimony followed by deprotonation of the intermediate-protonated radical affords the free base radicals [3-, 4-pyDTDA], the crystal structures of which, along with those of their diselenadiazolyl analogues [3-, 4-pyDSDA], have been characterized by powder or single-crystal X-ray diffraction. The crystal structures consist of "pancake" π-dimers linked head-to-tail into ribbonlike arrays by η2-S2---N(py) intermolecular secondary bonding interactions. Methylation of the persilylated (iso)nicotinimide-amides prior to condensation with sulfur monochloride leads to N-methylated double chloride salts Me[3-, 4-pyDTDA][Cl]2, which can be converted by metathesis into the corresponding triflates Me[3-, 4-pyDTDA][OTf]2 and then reduced to the N-methylated radical triflates Me[3-, 4-pyDTDA][OTf]. The crystal structures of both the N-methylated double triflate and radical triflate salts have been determined by single-crystal X-ray diffraction. The latter consist of trans-cofacial π-dimers strongly ion-paired with triflate anions. Variable temperature magnetic susceptibility measurements on both the neutral and radical ion dimers indicate that they are diamagnetic over the temperature range 2-300 K.

8.
Cryst Growth Des ; 18(5): 3151-3160, 2018 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-30258305

RESUMO

The major diastereomer formed in the Barbier-type metal-mediated allylation of d-mannose has previously been shown to adopt a perfectly linear conformation, both in solid state and in solution, resulting in the formation of hydrogen-bonded networks and subsequent aggregation from aqueous solution upon stirring. Here, a comprehensive study of the solid state structure of both the allylated d-mannose and its racemic form has been conducted. The binary melting point diagram of the system was determined by differential scanning calorimetry analysis, and the obtained results, along with structure determination by single crystal X-ray diffraction, confirmed that allylated mannose forms a true racemate. Further examination by powder X-ray diffraction and CP MAS 13C NMR spectroscopy revealed polymorphism both in the pure enantiomer and in the racemate. In addition, the propargylated and hydrogenated analogues of allylated d-mannose were prepared and subjected to thermal and spectroscopic analyses. The crystal structure of the propargylated compound was successfully determined, showing a linear molecular conformation similar to that found for allylated d-mannose. Both new compounds likewise display aggregation behavior in water, further verifying that the low-energy linear conformation plays a significant role in this unusual behavior of these rodlike mannose derivatives.

9.
Biomacromolecules ; 19(10): 3983-3993, 2018 10 08.
Artigo em Inglês | MEDLINE | ID: mdl-30207704

RESUMO

Pharmaceutical nanosuspensions are formed when drug crystals are suspended in aqueous media in the presence of stabilizers. This technology offers a convenient way to enhance the dissolution of poorly water-soluble drug compounds. The stabilizers exert their action through electrostatic or steric interactions, however, the molecular requirements of stabilizing agents have not been studied extensively. Here, four structurally related amphiphilic Janus-dendrimers were synthesized and screened to determine the roles of different macromolecular domains on the stabilization of drug crystals. Physical interaction and nanomilling experiments have substantiated that Janus-dendrimers with fourth generation hydrophilic dendrons were superior to third generation analogues and Poloxamer 188 in stabilizing indomethacin suspensions. Contact angle and surface plasmon resonance measurements support the hypothesis that Janus-dendrimers bind to indomethacin surfaces via hydrophobic interactions and that the number of hydrophobic alkyl tails determines the adsorption kinetics of the Janus-dendrimers. The results showed that amphiphilic Janus-dendrimers adsorb onto drug particles and thus can be used to provide steric stabilization against aggregation and recrystallization. The modular synthetic route for new amphiphilic Janus-dendrimers offers, thus, for the first time a versatile platform for stable general-use stabilizing agents of drug suspensions.


Assuntos
Dendrímeros/química , Indometacina/química , Poloxâmero/química , Tensoativos/química , Água/química , Interações Hidrofóbicas e Hidrofílicas , Suspensões
10.
Dalton Trans ; 46(39): 13582-13589, 2017 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-28952629

RESUMO

The synthesis and structural characterization of two benzoquinone-bridged dinuclear rare-earth complexes [BQ(MCl2·THF3)2] (BQ = 2,5-bisoxide-1,4-benzoquinone; M = Y (1), Dy (2)) are described. Of these reported metal complexes, the dysprosium analogue 2 is the first discrete bridged dinuclear lanthanide complex in which both metal centres reside in pentagonal bipyramidal environments. Interestingly, both complexes undergo significant thermal expansion upon heating from 120 K to 293 K as illustrated by single-crystal X-ray and powder diffraction experiments. AC magnetic susceptibility measurements reveal that 2 does not show the slow relation of magnetization in zero dc field. The absent of single-molecule behaviour in 2 arises from the rotation of the principal magnetic axis as compared to the pseudo-C5 axis of the pentagonal bipyramidal environment as suggested by ab initio calculations. The cyclic voltammetry and chemical reduction experiments demonstrated that complexes 1 and 2 can be reduced to radical species containing [BQ3˙-]. This study establishes efficient synthetic strategy to make bridged redox-active multinuclear lanthanide complexes with a pentagonal bipyramidal coordination environment that are potential precursors for single-molecule magnets.

11.
Chemistry ; 23(48): 11714-11718, 2017 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-28631856

RESUMO

Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag+ -complexes. Selective formation of discrete tetrameric I6 L4 and dimeric I3 L2 halonium cages, wherein multiple [N⋅⋅⋅I+ ⋅⋅⋅N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1-methyl-1-azonia-4-azabicyclo[2.2.2]octane)-mesitylene ligand, L1(PF6 )3 , and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I6 L14 (PF6 )18 and I3 L22 (PF6 )3 , were obtained through the [N⋅⋅⋅Ag+ ⋅⋅⋅N]→ [N⋅⋅⋅I+ ⋅⋅⋅N] cation exchange reaction between the corresponding Ag6 L14 (PF6 )18 and Ag3 L22 (PF6 )3 coordination cages, prepared as intermediates, and I2 . The synthesized metallo- and halonium cages were studied in solution by NMR, in gas phase by ESI-MS and in the solid-state by single crystal X-ray diffraction.

12.
Dalton Trans ; 46(22): 7309-7316, 2017 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-28547007

RESUMO

Simple ML2 [M = Fe(ii), Co(ii), Ni(ii)] complexes obtained from a perfluoroalkylamide derivative of 4-aminophenyl-2,2',6,2'-terpyridine spontaneously, yet anion selectively, self-assemble into gels, which manifest an unprecedented rapid gel strength recovery, viz. self-healing, and thermal rearrangement in aqueous dimethyl sulfoxide. The key factor for gelation and rheological properties emerges from the fluorine-fluorine interactions between the perfluorinated chains, as the corresponding hydrocarbon derivative did not form metallogels. The perfluoro-terpyridine ligand alone formed single crystals, while its Fe(ii), Co(ii) or Ni(ii) complexes underwent rapid gelation leading to highly entangled fibrillar networks visualized by electron microscopy. The thermodynamic parameters of gelation based on variable temperature NMR 1H and 19F resonances showed that gelation was enthalpically favourable and entropically disfavourable. The step strain rheological experiments revealed that the gels undergo rapid self-healing and the morphological features, thermal stability and mechanical properties were found to depend on the nature of the metal ion.

13.
Angew Chem Int Ed Engl ; 56(23): 6473-6477, 2017 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-28452396

RESUMO

The synthesis and spontaneous, reversible supracolloidal hydrogen bond-driven self-assembly of cobalt nanoparticles (CoNPs) into hollow shell-like capsids and their directed assembly to higher order superstructures is presented. CoNPs and capsids form in one step upon mixing dicobalt octacarbonyl (Co2 CO8 ) and p-aminobenzoic acid (pABA) in 1,2-dichlorobenzene using heating-up synthesis without additional catalysts or stabilizers. This leads to pABA capped CoNPs (core ca. 5 nm) with a narrow size distribution. They spontaneously assemble into tunable spherical capsids (d≈50-200 nm) with a few-layered shells, as driven by inter-nanoparticle hydrogen bonds thus warranting supracolloidal self-assembly. The capsids can be reversibly disassembled and reassembled by controlling the hydrogen bonds upon heating or solvent exchanges. The superparamagnetic nature of CoNPs allows magnetic-field-directed self-assembly of capsids to capsid chains due to an interplay of induced dipoles and inter-capsid hydrogen bonds. Finally, self-assembly on air-water interface furnishes lightweight colloidal framework films.

14.
Dalton Trans ; 45(32): 12691-701, 2016 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-27453403

RESUMO

A high-yield synthesis of [Li{S(H)C(PPh2S)2}]2 [Li2·(3)2] was developed and this reagent was used in metathesis with ZnCl2 and NiCl2 to produce homoleptic complexes 4 and 5b in 85 and 93% yields, respectively. The solid-state structure of the octahedral complex [Zn{S(H)C(PPh2S)2}2] (4) reveals notable inequivalence between the Zn-S(C) and Zn-S(P) contacts (2.274(1) Å vs. 2.842(1) and 2.884(1) Å, respectively). Two structural isomers of the homoleptic complex [Ni{S(H)C(PPh2S)2}2] were isolated after prolonged crystallization processes. The octahedral green Ni(ii) isomer 5a exhibits the two monoprotonated ligands bonded in a tridentate (S,S',S'') mode to the Ni(ii) centre with three distinctly different Ni-S bond lengths (2.3487(8), 2.4500(9) and 2.5953(10) Å). By contrast, in the red-brown square-planar complex 5b the two ligands are S,S'-chelated to Ni(ii) (d(Ni-S) = 2.165(2) and 2.195(2) Å) with one pendant PPh2S group. DFT calculations revealed that the energetic difference between singlet and triplet state octahedral and square-planar isomers of the Ni(ii) complex is essentially indistinguishable. Consistently, VT and (31)P CP/MAS NMR spectroscopic investigations indicated that a mixture of isomers exists in solution at room temperature, while the singlet state square-planar isomer 5b becomes favoured at -40 °C.

15.
J Colloid Interface Sci ; 438: 77-86, 2015 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-25454428

RESUMO

HYPOTHESIS: The microcrystalline fibers of N-(2-aminoethyl)-3α-hydroxy-5ß-cholan-24-amide 1 provided a useful model system for studying the complex relationship between morphology, experimental parameters, solvent, and the phenomenon of organogelation. The presence of solvents in the solid forms of 1 along with crystallization behavior suggested solvate formation and polymorphic behavior. EXPERIMENTS: Forty solid state- and xerogel samples of 1 formed in organic solvents and in three categories of experimental conditions were analyzed with single crystal X-ray diffraction (XRD), powder X-ray diffraction (PXRD), Raman microscopy, and attenuated total reflection Fourier-transform infrared spectroscopy (ATR FTIR). FINDINGS: Two polymorphs and four isostructural aromatic solvates of 1 were found among some unknown forms in the samples. Single crystal X-ray structures of one polymorph and bromobenzene solvate were obtained, the latter from a xerogel. Multiple crystal forms could be present in a sample, and their contributions to gelation were estimated taking the experimental conditions into account. Gelator 1 could act as a variable component gelator, either alone or in combination with an aromatic solvent. The research brings new insight into the structures of microcrystalline organogel fibers, linking solvate/inclusion crystal formation with microcrystalline fibers of an organogelator for the first time.

16.
Chem Commun (Camb) ; 50(41): 5469-72, 2014 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-24718313

RESUMO

Tripodal cationic N-donor ligands exhibit sterically controlled self-assembly of tetrahedral M6L4 coordination cages that promote selective anion encapsulation (PF6(-) > OTf(-)) in the solid state. The described method is a potential template for stepwise assembly of hetero-ligand coordination cages and polymers.

17.
Spectrochim Acta A Mol Biomol Spectrosc ; 117: 728-38, 2014 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-24140744

RESUMO

The discrete mixed [TeBrxCl6-x](2-) anions in their disordered crystal structures have been identified by using the phases prepared by the reaction of 1-butyl-2,3-dimethylimidazolium halogenides (bdmim)X with tellurium tetrahalogenides TeX4 (X=Cl, Br) as examples. Homoleptic (bdmim)2[TeX6] [X=Cl (1), Br (2)] and mixed (bdmim)2[TeBr2Cl4] (3), and (bdmim)2[TeBr4Cl2] (4) are formed depending on the choice of the reagents, and their crystal structures have been determined by single-crystal X-ray diffraction. The coordination environments of tellurium in all hexahalogenidotellurates are almost octahedral. Because of the crystallographic disorder, the mixed [TeBr2Cl4](2-) and [TeBr4Cl2](2-) anions in 3 and 4 cannot be identified in their crystal structures. Pawley refinement of the X-ray powder diffraction patterns of 1-4 indicates the presence of single phases in all four products. The solid state Raman spectra of 1-4 were assigned with help of DFT calculations that were performed both for the discrete anions in vacuum and for the complete crystal structures employing periodic boundary conditions. The fundamental vibrations of the homoleptic [TeX6](2-) (X=Cl, Br) anions could be well reproduced by the solid-state DFT computations and enabled a complete assignment of the Raman spectra. While the presence of cis-isomers in both [TeBr2Cl4](2-) and [TeBr4Cl2](2-) could be inferred by the computed fundamental vibrations, that of trans-isomers among the reaction products is, however, also possible. The pathway of the formation of [TeX4Y2](2-) isomers from TeX4 and Y(-) (X, Y=Cl, Br) was also explored by DFT calculations both in vacuum and in solution and indicated that both reactions afforded 80 mol% of cis-isomers and 20 mol% of trans-isomers.


Assuntos
Ânions/química , Brometos/química , Cloretos/química , Imidazóis/química , Teoria Quântica , Análise Espectral Raman , Telúrio/química , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Estrutura Molecular , Difração de Raios X
18.
Acta Crystallogr Sect E Struct Rep Online ; 69(Pt 5): o681, 2013 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-23723841

RESUMO

In the title compound, C15H16O2, the dihedral angle between the planes of the aromatic rings is 30.5 (2)°. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds and C-H⋯π inter-actions, forming a two-dimensional network lying parallel to (100).

19.
Acta Crystallogr Sect E Struct Rep Online ; 69(Pt 5): o810-1, 2013 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-23723948

RESUMO

In the title compound, C16H18O3, the dihedral angle between the benzene rings is 33.4 (2)°. In the crystal, mol-ecules are packed in a zigzag arrangement along the b-axis and are inter-connected via weak C-H⋯O hydrogen bonds, and C-H⋯π inter-actions involving the meth-oxy groups and the benzene rings of neighbouring molecules.

20.
Acta Crystallogr Sect E Struct Rep Online ; 69(Pt 4): o510-1, 2013 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-23634057

RESUMO

The title compound, C15H16O2, crystallizes with three independent mol-ecules in the asymmetric unit. The intra-molecular torsion angle between the aromatic rings of each mol-ecule are -36.4 (3), 41.3 (3) and -37.8 (3)°. In the crystal, the complicated packing of the mol-ecules forms wave-like layers along the b and c axes. The mol-ecules are connected via extensive meth-oxy-phenyl C-H⋯π inter-actions. A weak C-H⋯O hydrogen-bonding network also exists between meth-oxy O atoms and aromatic or meth-oxy H atoms.

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