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1.
Reactions that occur within or between molecular crystals, in particular those reactions that are activated by mechanical methods, are reviewed. The focus is on processes (whether intrasolid or intersolid) that are controlled primarily by supramolecular bonding, such as template cycloadditions, formation of inclusion compounds, reactions between molecular crystals by the reassembling of noncovalent bonds, and the formation of complexes and coordination compounds. It is proposed that solvent-free mechanochemical methods, for example, cogrinding, milling, and kneading, represent viable "green" routes for the preparation of novel molecular and supramolecular solids.  相似文献   

2.
Supramolecular reactions between crystalline materials as well as reactions between a crystalline material and a vapour can be used to generate new crystalline substances. These solvent-free processes can be exploited to prepare both hydrogen-bonded co-crystals and coordination networks. Solid-vapour reactions do not differ from solid-vapour uptake/release processes, and can also be used to prepare polymorphs and solvates. It is argued that solvent-less reactions involving molecular crystals represent a green route to supramolecular solid-state chemistry and crystal engineering.  相似文献   

3.
Traditionally, chemical reaction between solids has been considered to typically occur on a geological time scale without the benefit of high temperature, due to diffusion block in the solids. However, recent advancements have revealed that many solvent-free reactions between molecular crystals can quickly occur at room or near-room temperature. These reactions have raised a novel scientific question as to how the reactive species can overcome the diffusion-controlled kinetic limitations under such moderate conditions. From time-resolved powder UV-vis reflection spectra and optical micrographs with the reaction between dimethylglyoxime and Ni(Ac) 2.4H 2O and the reaction between hexamethylenetetramine and CoCl 2.6H 2O as models, we found that the solvent-free reaction really occurs at an intermediate state between the solid state and the liquid state. Formation of the liquid phase provides a convenient approach to diffusion of reactive species, whereas formation of a solid product layer hampered the transfer of reactive species. Both factors led to a broad reactive rate band in the long reaction region. The results have explained the diffusion mechanism of the fast reaction between the molecular crystals under moderate conditions.  相似文献   

4.
Supramolecular reactions between crystalline materials can be exploited to prepare both hydrogen bonded co-crystals and coordination networks. Mechanical mixing of molecular crystals as well as kneading provide an alternative, solvent-free, route to novel materials hence these methods represent a green route to supramolecular solid-state chemistry.  相似文献   

5.
Hydrophobicity and floatability of solids have been analyzed from the standpoint of properties of solid-water and solid-water vapors interfaces, chemical bonds, bulk properties, crystal structure of the solid, and reactivity of the solid with water. Although the hydrophobicity results from complex interactions in the solid-water-air system, simple equations and rules for predicting hydrophobicity and floatability are presented. The applicability of the Gaudin-Miaw-Spedden theory which states that molecular and sheet crystals, if their structure is controlled by the residual bonds across their basal planes, are floatable was confirmed. It was also shown that elements and compounds with different degrees of ionic-covalent and metallic-nonmetallic characters of bonds in the absence of residual bonds can be either hydrophilic, hydrophobic, or change their properties from hydrophobic to hydrophilic and vice versa. For some materials, hydrophobidty was found to be time-dependent. Decreasing hydrophobicity occurs with the oxidation and hydroxylation of the surface (oxides, metals), while increasing hydrophobicity takes place due to non-dissociative adsorption of water vapors on the surface (noble metals). Increased hydrophobicity can also be due to the formation of hydrophobic species such as sulfur species on the surface of Sulfides. It was demonstrated that the potential hydrophobicity of solids, expressed as the contact angle formed between the three involved (solid, water, and air) phases, can be evaluated from the Hamaker constants.This work supplements the Gaudin-Miaw-Spedden theory by showing that not only molecular crystals (paraffin, I2, S8, As4O6, As2S2) and non-ionic sheet crystals (MoS2, Sb2S3, talc, graphite, As2S3, boric acid, BN) but also elements and crystalline compounds without residual bonds can be hydrophobic and floatable. A partial list of such materials includes Hg, Ge, Si, SiC, AgI, CaF2, and diamond (whose hydrophobidties are already well known) as well as BaSO4, FeTiO3, In, and Sn (whose hydrophobidties have been established in this work). It was also demonstrated that the hydrophobidty of some solids changes as a result of reaction of the surface with constituents of the air.  相似文献   

6.
Hydrogen chloride gas (HCl) is absorbed (and reversibly released) by a nonporous crystalline solid, [CuCl2(3-Clpy)2] (3-Clpy = 3-chloropyridine), under ambient conditions leading to conversion from the blue coordination compound to the yellow salt (3-ClpyH)2[CuCl4]. These reactions require substantial motions within the crystalline solid including a change in the copper coordination environment from square planar to tetrahedral. This process also involves cleavage of the covalent bond of the gaseous molecules (H-Cl) and of coordination bonds of the molecular solid compound (Cu-N) and formation of N-H and Cu-Cl bonds. These reactions are not a single-crystal-to-single-crystal transformation; thus, the crystal structure determinations have been performed using X-ray powder diffraction. Importantly, we demonstrate that these reactions proceed in the absence of solvent or water vapor, ruling out the possibility of a water-assisted (microscopic recrystallization) mechanism, which is remarkable given all the structural changes needed for the process to take place. Gas-phase FTIR spectroscopy has permitted us to establish that this process is actually a solid-gas equilibrium, and time-resolved X-ray powder diffraction (both in situ and ex situ) has been used for the study of possible intermediates as well as the kinetics of the reaction.  相似文献   

7.
Mechanochemistry afforded a photoactive cocrystal via coexisting (B)O−H⋅⋅⋅N hydrogen bonds and B←N coordination. Specifically, solvent-free mechanochemical ball mill grinding and liquid-assisted grinding of a boronic acid and an alkene resulted in mixtures of hydrogen-bonded and coordinated complexes akin to mixtures of noncovalent complexes that can be obtained in solution in equilibria processes. The alkenes of the hydrogen-bonded assembly undergo an intermolecular [2+2] photodimerization in quantitative conversion, effectively reporting the outcome of the self-assembly processes. Our results suggest that interplay involving noncovalent bonds subjected to mechanochemical conditions can lead to functional solids where, in the current case, the structure composed of the weaker hydrogen bonding interactions predominates.  相似文献   

8.
Cyclooligomerization of 2,6-dichloropyrazine 4 and benzyl 2,3-dihydroxybenzoate 5 under microwave irradiation resulted in a racemic pair of ester functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 6, which was further transformed to the corresponding racemic carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 3. Both enantiomers of 3 adopt 1,3-alternate conformations with their two carboxylic acid groups pointing to opposite directions in the solid state. Enantiomers of 3 form a step-like one-dimensional supramolecular polymer via intermolecular hydrogen bond interactions between the carboxylic acids for crystals obtained in methanol. No hydrogen bonds were formed between the carboxylic acids for crystals of 3 obtained in pyridine and aqueous guanidine solutions; instead, intermolecular hydrogen bonds between the carboxylic acid groups of 3 and pyridine, as well as guanidinium ions were formed. Under metal-mediated self-assembly conditions, the pyrazinyl nitrogen atoms in 3 interacted with transition metal ions, such as Ag(I), Cu(II) and Zn(II), and resulted in the formation of four new metal-containing supramolecular complexes. Metallomacrocycles 7, 8 and 9 were formed by reactions of 3 with Ag(I) or Cu(II) ions by bridging two ligands 3 in the equatorial region via M-N coordination bonds. A one-dimensional coordination polymer 10 was generated by reaction between ligand 3 and Zn(II) ions, and a cage-based structure is presented in 10 by bridging of the cyclophane units by Zn(2+) ions via Zn-N and Zn-O bonds.  相似文献   

9.
Coordination-driven self-assembly: solids with bidirectional porosity   总被引:3,自引:0,他引:3  
Coordination-driven self-assembly reactions have been used in the preparation of a variety of discrete supramolecular species, some of which have shown promise as synthetic receptors. Many highly ordered coordination polymers and porous networks have been prepared in a similar fashion. While a few of these solids are capable of the uptake of small organic molecules in the resultant molecular channels, the formation of truly porous structures has frequently been thwarted by lattice interpenetration. A strategy for the formation of porous solids that may circumvent this problem is based on the covalent construction of nanoscale macrocycles which, when eclipsed in the solid state, may lead to porous, tubular assemblies. We have incorporated these concepts toward the realization of a bidirectionally porous solid. The metal-directed, self-assembly of a conjugated, macrocyclic ligand provides a discrete, supramolecular entity in solution and the solid state. X-ray crystallographic analysis establishes that this assembly packs such that bidirectional channels are realized, and the incorporation of only ClCH2CH2Cl into the crystal lattice demonstrates that these channels are potentially suitable for the selective uptake of small organic guests.  相似文献   

10.
The microwave-assisted hydrophosphinylation of propargyl alcohols has been investigated using group 9 catalysts under solvent-free conditions as well as with pure water, ethyl lactate, or THF as the solvent. Reactions involving simple propargyl alcohols gave mixtures containing significant amounts of elimination products. In contrast, analogous reactions involving ethynyl steroids afforded a single species with only trace amounts of elimination products. The molecular structures of several derivatives have been determined and are discussed.  相似文献   

11.
A tricyclic phosphine has been generated that has a rigid molecular backbone with the P atoms exclusively bound to C(sp2) atoms as well as a very large Tolman angle and buried volume. It is an interesting new ligand in coordination chemistry (Au, Pd complexes) and shows unusual insertion reactions into its endocyclic P?C bonds facilitated by its inherent molecular strain.  相似文献   

12.
Fractal structures are of fundamental importance in science, engineering, mathematics, and aesthetics. Construction of molecular fractals on surfaces can help to understand the formation mechanism of fractals and a series of achievements have been acquired in the preparation of molecular fractals. This review focuses on Sierpiński triangles (STs), representatives of various prototypical fractals, on surfaces. They are investigated by Monte Carlo simulations and ultra-high vacuum scanning tunneling microscopy. STs are bonded through halogen bonds, hydrogen bonds, metal-organic coordination bonds and covalent bonds. The coexistence of and competition between fractals and crystals are realized for a hydrogen-bonded system. Electronic properties of two types of STs are summarized.  相似文献   

13.
N- aryl substituted benzenesulfamides are often used as heating-sensitive recording material1, thermal printing material2, sensitizer3 and developer4. Moreover, some of the benzenesulfamides have antifungal activities5. Many methods have been described for preparation of sulfamides. They are used to carry out in solvent8 or in solid phase condition9. These methods required solvent or solid support and even required heating or cooling. At the same time, the process of these methods is complex. Now we have developed a new method to prepare N-aryl substituted toluenesulfamides under solvent-free conditions.In recent years, solvent-free technology has gained popularity in organic synthesis. For instance,solidstate reaction and microwave reaction have received considerable attention. Solvent-free synthesis of amides has been reported10-11. This technology has many advantages such as high efficiency and selectivity, easy separation and environmental acceptability. All these merits are in accord with green chemistry's requirements of energy-saving, high efficiency and environmental benefits.In our paper, we used a simple and efficient method for preparing N-aryl substituted toluenesulfamides under solvent-free conditions, as a replacement for classic solvent, which gives many environmental benefits.All reactions were completed at room temperature by co-grinding in an agate mortar for 3-20min and the results are shown in Table 1.In conclusion, we have developed an efficient and convenient method of preparation N-aryl substituted toluenesulfamides in high yields. It symbols an improvement for synthesis of benzenesulfamides.  相似文献   

14.
The mesoscale design of domain assembly is crucial for controlling the bulk properties of solids. Herein, we propose a modular design of domain assembly in porous coordination polymer crystals via exquisite control of the kinetics of the crystal formation process. Employing precursors of comparable chemical reactivity affords the preparation of homogeneous solid-solution type crystals. Employing precursors of distinct chemical reactivity affords the preparation of heterogeneous phase separated crystals. We have utilized this reactivity-directed crystallization process for the facile synthesis of mesoscale architecture which are either solid-solution or phase-separated type crystals. This approach can be also adapted to ternary phase-separated type crystals from one-pot reaction. Phase-separated type frameworks possess unique gas adsorption properties that are not observed in single-phasic compounds. The results shed light on the importance of crystal formation kinetics for control of mesoscale domains in order to create porous solids with unique cooperative functionality.  相似文献   

15.
A solvent-free photooxygenation process that uses organic substrates embedded in porphyrin-loaded polystyrene beads as solid support is described and applied for ene- and [4 + 2]-cycloaddition reactions involving singlet oxygen (1 delta g).  相似文献   

16.
It is a common practice to approximate the desorption rate of atoms from crystal surfaces with an expression of the form nueff exp(-DeltaE/kBT), where DeltaE is an activation barrier to desorb and nueff is an effective vibrational frequency approximately 10(12) s(-1). For molecular solids, however, such an approximation can lead to a many orders of magnitude underestimation of vapor pressure and sublimation rates due to neglected contributions from molecular internal degrees of freedom. Here, we develop a simple working formula that yields good estimates for a general molecular (or atomic) solid and illustrate the approach by computing equilibrium vapor pressure of three different molecular solids and an atomic solid, as well as the desorption rate of a foreign (inhibitor) molecule from the surface of a molecular solid.  相似文献   

17.
The structures of mixed crystals — solid solutions in the peganole-brompeganole system with molar ratios 0.72:0.28, 0.32:0.68, 0.10:0.90 and of pure peganole are determined by single crystal X-ray diffraction. It is shown that the solid solutions (mixed crystals) exist as three different phases. These crystal structures tend to form closed centrosymmetric dimers involving two molecules (probably different) joined by “anti-parallel” centrosymmetric hydrogen O-H...N(1) bonds. The development of this dimer is the cause of forming mixed crystals in the peganole–brompeganole system.  相似文献   

18.
A simple, green and efficient protocol was developed using β-cyclodextrin as a solid catalyst for the solvent-free synthesis of various Biginelli adducts. The advantages of our protocol included the following: (i) a metal-free methodology; (ii) high yields; (iii) simple and efficient work-up procedures; (iv) improved results under solvent-free conditions. β-cyclodextrin-catalyzed the Biginelli reactions for various aldehydes, demonstrating that it is an efficient and eco-friendly catalyst for the preparation of heterocyclic compounds.  相似文献   

19.
An important stage in process development is kilo scale preparation of the target compound. For this reason, a procedure involving water-based biphasic reaction media has been developed for conducting some exothermic reactions on a large scale. This protocol is illustrated by the energy-efficient and rapid preparation of dihydropyrimidinones by a solvent-free, green chemistry procedure applied to the Biginelli reaction using p-toluenesulfonic acid as catalyst.  相似文献   

20.
Crystal Engineering has traditionally dealt with molecular crystals. It is the understanding of intermolecular interactions in the context of crystal packing and in the utilization of such understanding in the design of new solids with desired physical and chemical properties. We outline here five areas which come under the umbrella of Crystal Engineering and where we feel that a proper planning of research efforts could lead to higher dividends for science together with greater returns for humankind. We touch on themes and domains where science funding and translation efforts could be directed in the current climate of a society that increasingly expects applications and utility products from science and technology. The five topics are: 1) pharmaceutical solids; 2) industrial solid state reactions; 3) mechanical properties with practical applications; 4) MOFs and COFs framework solids; 5) new materials for solar energy harvesting and advanced polymers.  相似文献   

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