Retention times tr and arithmetic retention indices IA of di (n‐ and iso‐nonyl)cyclohexane‐1,2‐dicarboxylates.
\r\n\tWith this goal in mind, together with the US Prof. John M. Ballato and the InechOpen publishing house since 2011 we have published in 2011, 2013, 2015 and 2017 4 books of our serial “Optoelectronics” and the book “Excitons”, edited in 2018 by Prof. Sergei L. Pyshkin. Publishing the new book “Luminescence” we are pleased to note the growing number of countries participating in this undertaking as well as for a long time fruitfully cooperating scientists from the United States and the Republic of Moldova.
\r\n\tSpecialists from all over the world have published in edited by us books their works in the field of research of the luminescent properties of various materials suitable for use in optoelectronic devices, the development of new structures and the results of their application in practice.
Di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylate (DINCH) isomers are considered to be relatively safe substitutes of the corresponding phthalates, especially when used in the manufacturing of various medical devices and toys. For this reason there is a great interest in the analysis of their isomers by different analytical methods.
\nIn this chapter, we present the results of the application of the different modern chromatographic and spectrometric analytical techniques, such as gas chromatography (GC), electrospray‐mass spectrometry (ESI/MS), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), gas chromatography‐mass spectrometry (GC/MS), and others similar ones to the identification of the new generation additives.
\nThey were obtained in the catalytic hydrogenation reactions in the presence of the Ni catalyst and used as plasticizers and cross‐linking agents to some polymers, such as poly(vinyl chloride) (PVC) or epoxy resins.
\nDi(alkyl) esters of 1,2‐benzene dicarboxylic acid of higher molecular weight, such as di(2‐ethylhexyl)phthalate (DEPH) or di(isononyl)phthalate (DINP), are widely used as plasticizers in the processing of various types of polymers, especially poly(vinyl chloride). These types of compounds are not chemically bound to the polymers, so they are gradually released from them by volatilization from the surface into the air, or by migration due to contact with a solid, or by extraction from the polymer into a liquid also due to direct contact [1]. These compounds are becoming challenging environmental pollutants with a strong impact on the human health. The toxicity effects of these compounds have been intensively investigated, and within the last decade some of those compounds have been classified as endocrine disruptors [2] and potential carcinogens [3–6]. The metabolism of DINP in animals [7] and in humans [8, 9] has been studied. In these studies, where deuterium‐labeled DINP was used, samples of animal and human urine were found to contain monoester of mono‐iso‐nonylphthalate and its oxidized isomers containing hydroxy, oxo, and carboxy functional groups as metabolites of DINP.
\nThe new di(alkyl)cyclohexane 1,2 dicarboxylates (DINCH) plasticizers may be used to improve the flexibility of some polymers, mainly PVC. They also have less toxic effect on human health when compared to di(alkyl)phthalates.
\nCyclohexanedicarboxylic esters are produced through the catalytic hydrogenation of corresponding phthalates or through the Diels‐Alder reaction of maleic acid esters with ethylene followed by hydrogenation using supported nickel catalyst [10].
\nDi(n‐ and isoalkyl(C4–C9)) phthalates were synthesized in the esterification reaction of phthalic anhydride with appropriate aliphatic alcohol using an optimized procedure [11, 12]. Hydrogenation of these esters, after their prior purification by distillation, were carried out in a high pressure reactor in the presence of the Ni catalyst on aluminosilicate support at 150°C for 3.0 h and under 9.0 MPa hydrogen pressure, according to the following scheme:
\nwhere R = alkyl (C4 – C9).
\nDuring the hydrogenation reaction of di(alkyl)phthalates, cis and trans isomers of the di(alkyl(C4–C9))cyclohexane‐1,2‐dicarboxylates are formed as the main products with a yield of 98.0%.
\nIdentification of cis and trans isomers of the synthesized di(n‐ and iso‐nonyl)cyclohexane‐1,2‐dicarboxylates was done by chromatographic and spectrometric methods of GC/MS and ESI/MS.
\nChromatographic separation of the compounds investigated and registration of their “electron impact” mass spectra (EIMS) was done by use of a gas chromatograph HP 6890 Series GC System (Hewlett‐Packard, Palo Alto, CA, USA) equipped with HP 5973 Network quadrupole mass selective spectrometric detector (Agilent Technologies, Palo Alto, CA, USA). Each sample was dissolved in CHCl3 to 5,0% solution. Then 0.1 μL of that solution was injected by using Hamilton microsyringe to the split/splitless injector (split mode 100:1) kept at 350°C. The fused silica capillary column HP 50+ (30.0 m length, internal diameter 0.2 mm and 0.2 μm phase film thickness) was heated in the range of 70–290°C with programmed temperature ramp 7°C/min. As a carrier gas helium (ultra‐pure, 99,999%) was used.
\nGC/MS was applied to analyze the synthesized cis and trans isomers of di(n‐ and isononyl) esters of 1,2‐cyclohexanedicarboxylic acid in order to get their good chromatographic separation enabling to record their electron impact (EI) mass spectra and also to calculate their arithmetic retention indices IA on the basis of their retention times tr.
\nFigure 1 shows an example of a chromatogram of cis (compound a1) and trans (compound a2) of the di(3,5,5‐trimethylhexyl) esters of cyclohexane‐1,2‐dicarboxylic acid as the reaction products of di(3,5,5‐trimethylhexyl)phthalate hydrogenation. Values of the retention times tr of the cis and trans isomers of the esters are always lower than those of the corresponding phthalates.
\nGC/MS chromatogram of cis (a1) and trans (a2) isomers of di(3,5,5-trimethylhexyl)cyclohexane-1,2-dicarboxy-late.
On the basis of the retention times tr of all analyzed cis and trans isomers and the retention times of a standard mixture of n‐alkanes C20–C40, the arithmetic retention indices (IA) were calculated using the following formulae (1) [13]:\n
where Ti, Tz, and Tz + 1 are the retention times of the analyzed component and neighboring n‐alkanes containing z and z + 1 carbon atoms, wherein Tz < Ti < Tz + 1
\nThe obtained values of IA for the analyzed compounds are given in Table 1.
\nThe linear relationship was found between the values of arithmetic retention indices IA of di(n‐alkyl(C4–C9))phthalates and the number of carbon atoms present in the alkyl substituents of esters obtained during the hydrogenation of appropriate phthalates [12].
\nThe values of IA of di(n‐alkyl(C4–C9)) phthalates are higher than those of their hydrogenation products. In both cases there is also a regularity according to which the esters with the longer alkyl substituents have the greater values of the arithmetic retention indices IA. Whereas in the case of the esters with branched alkyl chains of the substituents, their retention times tr and arithmetic retention indices IA have lower values compared to those of the corresponding esters with straight chain substituents. The values of their retention times are arranged in the following order: tra1,a2 < trb1,b2 < trc1,c2 and, similarly, the arithmetic retention indices are arranged in the following order: IA1,A2 < IB1,B2 < IC1,C2.
\nThe obtained tr and IA reference GC parameters for the analyzed cis and trans isomers of the di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates can be used for the unambiguous determination of the chemical structure of this type of organic compounds, particularly when both are present in the reaction product of the hydrogenation of di(n‐ and isononyl)phthalic acid esters. They may also be very useful for ongoing optimization of the technological parameters of the hydrogenation process using only the GC method.
\nCompound | \nName of compound | \nMol. weight [g/mol] | \nRetention time, tr [min] | \nArithmetic retention index, IA | \n
---|---|---|---|---|
a1 | \nDi(3,5,5‐trimethylhexyl)cyclohexane‐1,2‐dicarboxylic acid (cis isomer) | \n424 | \n33.81 | \n2780.0 | \n
a2 | \nDi(3,5,5‐trimethylhexyl)cyclo‐hexane‐1,2‐dicarboxylic acid (trans isomer) | \n424 | \n34.00 | \n2798.1 | \n
A | \nDi(3,5,5‐trimethylhexyl)phthalate | \n418 | \n35.94 | \n2976.9 | \n
b1 | \nDi(2-methyloctyl)cyclohexane-1,2-dicarboxylic acid (cis isomer) | \n424 | \n34.51 | \n2846.7 | \n
b2 | \nDi(2-methyloctyl)cyclohexane-1,2-dicarboxylic acid (trans isomer) | \n424 | \n34.68 | \n2862.9 | \n
B | \nDi(2‐methyloctyl)phthalate | \n418 | \n37.05 | \n3067.5 | \n
c1 | \nDi(n‐nonyl)cyclohexane‐1,2‐dicarboxylic acid (cis isomer) | \n424 | \n37.14 | \n3074.6 | \n
c2 | \nDi(n‐nonyl)cyclohexane‐1,2‐dicarboxylic acid (trans isomer) | \n424 | \n37.33 | \n3089.7 | \n
C | \nDi(n‐nonyl)phthalate | \n418 | \n39.85 | \n3257.6 | \n
Retention times tr and arithmetic retention indices IA of di (n‐ and iso‐nonyl)cyclohexane‐1,2‐dicarboxylates.
The good chromatographic separation in the GC/MS analysis of the cis and trans isomers of di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates enabled recording of their low‐resolution EI mass spectra, which are different for each isomer, and as such could be used for unambiguous identification of their chemical structures.
\nTable 2 gives the relative intensities of the most characteristic peaks of the molecular and fragment ions of all analyzed cis and trans isomers of di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates. In all mass spectra of these isomers there are low intensity peaks of their molecular ions [M]+• present at m/z 424, which allow to unambiguously determine the molecular weights of these compounds. Also, their mass spectra have a number of peaks referring to the characteristic fragment ions. The most intense characteristic peak of the fragmentation ion is easily recognized in the mass spectra of all analyzed esters (except the cis and trans isomers of di(3,5,5‐trimethylhexyl)cyclohexane‐1,2‐dicarboxylates—compounds a1 and a2). It occurs at m/z 155 and corresponds to the structure of the protonated anhydride of cyclohexane‐1,2‐dicarboxylic acid [11, 12]. However, in the mass spectra of the cis and trans isomers of compounds a1 and a2, in which isoalkyl substituents are more branched, as compared to other isomers—compounds b1, b2, c1, and c2 (Tables 1 and 2), the main peak corresponding to the ion at m/z 57 has the structure of [C(CH3)3]+. It is formed as a result of a homolytic cleavage of the single C–C bond located at the branched carbon atom of the alkyl substituent. The cleavage of the weaker C–C bond occurs more easily than in the other molecular ions [M]+• of the cis and trans isomers of the esters investigated, and it is the reason of the formation of the less intense ion at m/z 155 (also formed from the [M−9H19]+ ion as a result of the elimination of alkoxy radical •OC9H19 from the molecular ion [M]+• of these compounds). In general, the peak at m/z 155 may be used as a diagnostic peak for the unique identification of such type of esters, similarly as the peak at m/z 149, the main ion peak of di(alkyl)phthalates (except di(methyl)phthalate). The ion at m/z 149 has the structure of the protonated anhydride of phthalic acid [14–16].
\nRelative ion intensities [A1] of cis and trans isomers of di(n- and iso-nonyl)cyclohexane-1,2‐dicarboxylates in their mass spectra.
Other peaks present in all the MS spectra of the analyzed cis and trans isomers—compounds a1, a2, b1, b2, c1, and c2—correspond to the characteristic fragment ions formed by the cleavage of single C—C and CO bonds of their molecular ions [M]+•. These fragmentation reactions are accompanied by the transfer of hydrogen atoms in the McLafferty rearrangement together with an elimination of the neutral molecules of H2O and CO (Table 2).
\nFigures 2a and 2b show the mass spectra of isomers cis and trans of di(3,5,5-trimethylhexyl)cyclohexane)‐1,2‐dicarboxylic acid.
\nThe differences between EI mass spectra observed in all the analyzed compounds result both from different structures of the alkyl substituents of carboxyl groups of cyclohexane‐1,2‐dicarboxylic acids and from cis and trans isomerization being the result of the presence of cyclohexane ring in these esters.
\nMass spectrum of compound a1 (Figure 1): di(3,5,5-trimethylhexyl)cyclohexane-1,2‐dicarboxylate – cis isomer.
Mass spectrum of compound a2 (Figure 1) di(3,5,5‐trimethylhexyl)cyclohexane‐1,2‐dicarboxylate – trans isomer.
Electrospray ionization, being a “soft” ionization technique, was used in mass spectrometry (ESI/MS) for the identification of volatile samples of di(3,5,5‐trimethylhexyl)‐, di(2‐methyloctyl)‐, and di(n‐nonyl)cyclohexane‐1,2‐dicarboxylates. Each ESI mass spectrum of the compound investigated represents a mixture of cis and trans isomers of the same compound, and for this reason it cannot be used for their individual identification.
\nIn ESI/MS analysis the samples of di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates were dissolved in methanol (HPLC grade, J.T. Baker) and diluted with the same solvent to 1:40,000 (which corresponds to ca. 10 μM). All measurements were performed on an AB Sciex Q-TRAP® 4000 series hybrid quadrupole mass spectrometer equipped with electrospray ion source. Collision gas was nitrogen at the nominal pressure 3.2 × 10−5 Torr.
\nThe typical ESI mass spectrum of these compounds is shown in Figure 3. It presents a mixture of the fragment ion peaks of cis and trans isomers of di(3,5,5‐trimethylhexyl)cyclohexane‐1,2‐dicarboxylates and only has fewer peaks of mass fragmentation ions in comparison with the individual EI mass spectra (Figures 2a and 2b).
\nIn all the ESI mass spectra of these types of compounds, the peaks of quasi‐molecular ions [M+H]+ are present at m/z 425 and they are formed by the addition of hydrogen cation. They arise from both cis and trans isomers. More information about the fragment ions could be obtained from the interpretation of ESI mass spectra in which they derived from mass transitions: from [M+H]+ ions at m/z 281, after the cleavage of one of the unbranched or branched alkyl(C9) substituents and following neutral loss of H2O molecule leading to a fragment ion of m/z 155. The first transition is the most sensitive, and therefore it may be used to quantify di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates. The second transition was used only to confirm the results of the first one.
\nThe choice of selected characteristic ions for this type of compounds, for example, with an m/z of 155, present in other MS spectra of di[n‐ and isoalkyl(C4–C9)]cyclohexane‐1,2‐dicarboxylates, may be very helpful for their detection during ESI/MS analysis of one or more of the investigated compounds in complex matrices (e.g., PVC) and may also be very useful for quantitative assessment of the level of their actual impact on the human health.
\nFigure 4 shows a general mass fragmentation scheme of molecular ions [M]+ of di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates developed on the basis of the data obtained from their mass transitions. It describes a specific type of fragmentation reactions for this type of compounds as contrasted to the phthalic acid esters. The basic knowledge about their behavior during ionization of this type of compounds will make the interpretation of their mass spectra easier and will enable optimization of the methods of their quantification during the analysis of their release from polymers.
\nThe good chromatographic separation during GC/MS analysis of cis and trans isomers of di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates investigated enables the recording of their low‐resolution EI mass spectra, which are different from each other and thus can be used for unambiguous identification of their individual chemical structures. Also, chromatographic data, such as the values of retention times tr and arithmetic retention indices IA, are very useful in their identification, even when the reference substances are not available. The ESI/MS mode was shown to be successful in the determination of cis and trans isomers of the analyzed esters present in complex matrices of a polymer.
\nThe presented GC, GC/MS, and ESI/MS results for the representatives of the cis and trans isomers of some of the DINCH group of compounds may also be helpful in the determination of the chemical structures of their metabolites.
\nESI mass spectrum of cis and trans isomers of di(3,5,5‐ trimethylhexyl)cyclohexane‐1,2‐dicarboxylate.
General mass fragmentation scheme of molecular ions [M]+ of di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates.
Epoxy resins due to their excellent mechanical and dielectric properties along with relatively low shrinkage, high resistance to elevated temperatures, and chemical media, but also the ease of processing are extensively applied in many fields, such as adhesives, coatings, and construction materials. This flexibility of properties of epoxy‐ derived materials is achieved due to the resins’ tendency to undergo various modifications, usually by reactive and nonreactive fillers and different types of cross‐linking agents [17, 18]. The curing of epoxy resins involves the formation of rigid three‐dimensional network by reaction with cross‐linking agents possessing usually more than two functional groups. High cross‐linking density of epoxy systems is responsible for high impact strength of hardened epoxy resins and also at the same time for their inherent brittleness. Recently, lots of valuable papers have been published on modifications of epoxy resins, where incorporation of highly branched flexible modifiers considerably improved the mechanical behavior of epoxy materials [19–21]. Currently, hyperbranched polymers (HBPs) are of the biggest interest among all polymeric modifiers for epoxy resins. Branched structures of these resins are attractive due to their low viscosity and good ratio of reactive groups to molecular mass, especially when they are compared to their linear homologs. This makes HBPs perfect potential candidates as cross‐linking agents for epoxy resins. Knowing the influence of branching and functionality of hyperbranched polymers on material\'s characteristics can be used to tailor its final properties [22, 23].
\nThe hyperbranched poly(amines) may be used as specific additives as modifiers of the physicochemical properties of the epoxy resins. Especially, branched poly(amines) such as (N,N,N‐tri(3‐aminopropyl)amine and (N,N,N′,N′‐tetra(3‐aminopropyl) ethylene‐diamines may be used as specific additives—cross‐linking agents for this type of resins.
\nHyperbranched polymers can be prepared by various stepwise and repetitive chemical routes within which convergent and divergent methods are of the biggest practical meaning [24–26]. One of the easiest and the most effective way to synthesize the hyperbranched polyamines is cyanoethylation of primary amines followed by hydrogenation of resulting nitriles to generate primary amines. This process consists of an initial Michael’s addition of a core amine to acrylonitrile, and then in the presence of Raney nickel hydrogenation to core amine, which can be further processed in a stepwise manner. Katriztky et al. [27] synthesized various nitriles with the addition of acetic acid as a catalyst with yields reaching 90% but then failed to obtain pure primary amines in hydrogenation process over Raney nickel catalyst with the addition of ammonia in methanol, preventing from formation of secondary amino functionality. Buhleier et al. [28] by means of NaBH4∙CoCl2 reduced nitrile in 24% yield. After 15 years, this process was modified by using diisobutylaluminium hydride in a mixed solvent system of THF and hexane [29]. Worner and Mülhaupt performed hydrogenation of nitriles over Raney nickel in the presence of sodium hydroxide as a cocatalyst, which led to a decrease in reaction yield (ca. 70%) due to the retro‐Michael reaction caused by the action of a strong base [30].
\nDe Brabander‐van der Berg and Meijer reported successful hydrogenation over Raney cobalt catalyst in water under H2 pressure of 30–70 bar. Under these conditions no side products were obtained and 99.5% selectivity level per conversion was achieved [31].
\nThe cross‐linking agents (N,N,N‐tri(3‐aminopropyl)amine and (N,N,N′,N′‐tetra(3‐aminopropyl)ethylenediamines were obtained in the catalytic hydrogenation process of appropriate poly(nitriles) in the presence of modified silica support Ni catalyst.
\nPreparation of N,N,N‐tricyanoethylamine (TCA) and N,N,N′,N′‐tetracyanoethyl‐1,2‐ethylenediamine (TCED) was performed by means of bimolecular Michael addition of acrylonitrile to ammonia and ethylenediamine, respectively. The exotermic reaction of poly(nitriles) intermediates TCA and TCED starts with an addition of excessive acrylonitrile to the appropriate amine under ambient conditions.
\nThe poly(nitriles) used for hydrogenation process were synthesized in the reaction of 30% water solution of ammonia or 1,2‐ethylenediamine containing 1,4‐dioxane and ionic liquid with an excessive amount of acrylonitrile. When the reaction was completed at 60°C, poly(nitriles) were separated by means of a separatory funnel and dried over magnesium sulfate in order to remove any traces of water.
\nThe synthesized poly(nitriles) are the substrates in the hydrogenation reaction to obtain the primary poly(amines). This reaction was carried out in the presence of the Ni catalyst in the high‐pressure autoclave giving the final product of the polyamines—(N,N,N‐tri(3‐amino‐propyl)amine) (TAA) or (N,N,N′,N′‐tetra(3‐aminopropyl)‐ethylenediamine)) (TAED) with 82.0% and 88.0% yields, respectively.
\nPoly(nitriles) used for hydrogenation reaction were obtained in a cyanoethylation process, as shown in Figure 5 without purification procedures.
\nCyanoethylation of ammonia and 1,2 ethylenediamine to N,N,N tricyanoethylamine (TCA) — 3 and N,N,N’,N’ tetracyanoethylo 1,2 ethylenediamine (TCED) 4 followed by their hydrogenation reaction gives (N,N,N tri(3 aminopropyl)amine) (TAA) — 5 and (N,N,N’,N’ tetra(3 aminopropyl)ethylenediamine)) (TAED) — 6, respectively.
The hydrogenation reactions were carried out at 135°C, under 10 bars for 6 h. In the case of TAA synthesis, yield of this reaction reached 85.7%, while for TAED exceeded 82%.
\nIn case of hydrogenation of TCA for 0.14 mol of nitrile, 0.42 mol of H2 is needed for total conversion of nitrile groups into primary amino groups. It was determined that to achieve full conversion of poly(nitriles) to the poly(amines) seven cycles of refilling hydrogen were necessary, which equaled to 0.42 mol of H2. Exactly the same procedure was applied for hydrogenation of TCED, but full nitrile reduction was achieved after 12 cycles of hydrogen refill. In this case 0.72 mol of hydrogen was needed for the completion of the hydrogenation process (Figure 6).
\nHydrogenolysis of the TCA to N,N‐diaminepropylamine and n‐propylamine.
In order to identify poly(amines) as the hydrogenation reaction products of the poly(nitriles), GC/MS, FTIR, and 1H NMR instrumental analytical techniques were used.
\nGC/MS analyses of the branched polyamines were done by use of a gas chromatograph HP 6890 Series GC System (Hewlett‐Packard) equipped with HP 5973 Network quadrupole mass selective spectrometric detector (Agilent Technologies) in a similar way as it was described in Section 2.3.1.
\nHydrogenation process of TCED leads to the formation of N,N,N′‐triaminepropyl‐1,2‐ethylenediamine with retention time tr =19.61 min and N,N,N′,N′‐tetraaminepropyl‐1,2‐ethylenediamine (TAED) with tr = 23.60 min and small amounts of undesired by-products, which peaks are shown in Figure 7. In this reaction mixtures, besides the main products—components B and C, n‐propylamine (component A) with tr =2.31 min is present. The mechanism of its formation probably is either by hydrogenolysis or retro‐Michael reaction in which main products decomposes into molecules with lower molecular weights.
\nThe standard Fourier Transform Infrared Spectrometer Nicolet 6700 type (FTIR) equipped with operating software Omnic from Thermo Company was used for the qualitative determination of the functional groups occurring in the hydrogenation reaction products. FTIR spectra were registered in the range of 4000–650 cm−1 with the resolution of 4 cm−1.
\nChromatogram of the typical mixture of the hydrogenation products of N,N,N’,N’ tetracyanoethyl 1,2 ethylenediamine (TCED). GC peaks refer to: (A) n-propylamine; solvent — 1,4-dioxane; (B) N,N,N’ triaminepropyl-1,2-ethylenediamine; (C) N,N,N’,N’ tetraaminepropyl-1,2-ethylenediamine.
In the FTIR spectra (Figure 8) of the TCA and TCED there is apparent peak at 2250 cm−1 assigned to C≡N group. In their FTIR spectra, after hydrogenation reaction of TCA and TCED nitriles in these groups almost completely disappeared, and instead broad peaks around 3350 cm−1 assigned to N—H bonds in primary amino groups are observed.
\nFTIR spectra of nitriles derived from ammonia (TCA) and ethylenediamine (TCED) and their hydrogenated products TAA and TAED.
For 1H NMR analyses the NMR Bruker Ultrashield was used. All spectra were taken at the frequency of 400 MHz, CDCl3 with 0.03% TMS (v/v) was used as a solvent. Qualitative analyses were performed by using the Bruker Topspin 1 software.
\nThe structures of final products after hydrogenation reactions were confirmed by use of 1H NMR techniques. On the spectra recorded for TAA and TAED, there are shifts that could be assigned to protons corresponding to amine groups, meaning that the “core” molecules, ammonia and ethylenediamine, respectively, were successfully subjected to cyanoethylation reaction by acrylonitrile molecules.
\nThe signals observed in the 1H NMR spectra of TAA and TAED compounds (Figure 9) were taken to confirm their structures.
\n1H NMR (CDCl3) spectra of TAA (above) and TAED (below).
In the case of TAA: 0.98 ppm, s, 6H, –NH2; 1.50 ppm, p, –CH2–CH2; 1.70 ppm, t, 6H, N–CH2–CH2, 2.70 ppm, t, 6H, –CH2–NH2.
\nIn the case of TAED: 1.36 ppm, s, 8H, –NH2; 1.60 ppm, p, –CH2–CH2; 2.46 ppm, t, 8H, N–CH2–CH2, 2.50 ppm, s, 4H, N–CH2–CH2–N, 2.75 ppm, t, 8H, –CH2–NH2.
\nDuring hydrogenation process undesired reactions take place, leading to the formation of low‐molecular weight products. After hydrogenation of poly(nitriles), besides the main products being TAA and TAED, the n‐butylamine is one of the most abundant by- products present in the reaction mixture. It is formed by cleavage of bond between nitrogen heteroatom and β‐carbon atom from acrylonitrile.
\nNew generation additives for polymers such as plasticizers and cross‐linking agents were synthesized in the catalytic hydrogenation process in the presence of Ni catalyst.
\nAll hydrogenation products were analyzed using different analytical instrumental techniques such as GC/MS, ESI/MS, and spectroscopic techniques (e.g., 1H NMR).
\nThe new generation of plasticizers such as di(n‐ and isononyl)cyclohexane‐1,2‐dicarboxylates (DINCH components) are the new group of specific and safe plasticizers applied as the substitutes of di(alkyl) phthalates, especially di(2‐ethylhexyl) phthalate (DEHP) and di(n‐ and isononyl) phthalates in polymers.
\nThe identification of these compounds permits us to determine both the structures of the main products and their by-products as well. Cis and trans isomers of the cyclohexane-1,2-dicarboxylates may be applied to the identification of some DINCH constituents extracted from polymers and also in the elucidation of their structures in the human metabolites. ESI/MS mode analysis of these compounds and the knowledge about their mass fragmentation enable their detection, although without differentiation between individual cis and trans isomers. The obtained identification results concerning the determination of the individual chemical structures of some cis and trans di(n‐ and isoalkyl(C4–C9))cyclohexane‐1,2‐dicarboxylates isomers (DINCH) maybe used in their determination of exposure and risk assessments.
\nAlso, poly(amines) possessing usually more than two functional groups are very useful as cross‐linking agents and are used in the modification of physicochemical properties of the epoxy resins by the most effective chemicals.
\nThe obtained results from the analysis of the final product of hydrogenation reaction of both cis and trans di(n‐ and isoalkyl(C4–C9))cyclohexane‐1,2‐dicarboxylates isomers (DINCH) and branched poly(amines) are useful in the optimization of processes of their production in an industrial scale.
\nThe part of this work was realized within the INNTECH Project “New generation of cross‐linking agents for epoxy resins.” Research was sponsored by The National Centre for Research and Development under grant no INNOTECH‐K1/IN1/49/150947/NCBR/12. The authors would like to thank Dr. B. Poźniak and I. Semeniuk (M.Sc.) for spectrometric analyses of some hydrogenation products.
\nTo design a crystalline material that contains both chirality and porosity in to one framework is still a big challenge [1]. There are many inorganic frameworks with chiral crystal structures and some zeolite frameworks like LTJ, ITQ-37, CZP, BEA, SFS and STW have intrinsic chirality but their synthesis is full of challenges [1, 2, 3]. So far, different chiral induction methods and chiral structure directing agents has been applied to transfer chirality in inorganic frameworks but all of them have a limited success [1, 4]. In contrast to the traditional chiral materials as mentioned above, there are two emerging classes of chiral porous materials known as metal organic frameworks (MOFs) and covalent organic frameworks (COFs) that can be efficiently tailored to induce chirality for asymmetric catalysis and enantiomeric separation. As compared to the zeolite syntheses, homochiral MOFs/COFs can be efficiently constructed using chiral molecules as primary linkers or as supplementary or auxiliary ligands [5]. Herein, we will focus on recent advances in the syntheses of chiral microporous MOFs and COFs, their different properties and application e.g., enantioselective adsorption [6], chiral chromatographic resolution [7, 8], membrane separation [9], their specific structures and advantages over the traditional chiral materials.
Two aspects are notable while discussing chirality in solid materials; either the components of the framework are chiral, or the arrangement of the components in the solid framework is chiral [10]. For the development of chiral materials different strategies have been used, which include the introduction of chiral ligands or chiral templates, control of the chiral physical environment, and post-synthetic modification of the organic struts or the metal nodes through guest exchange [11, 12]. So the three most commonly used strategies for synthesizing homo-chiral microporous materials are, direct synthesis, chirality induction synthesis and post-synthetic modification [13]. Among these, the most successful strategy is to use enantiopure organic linkers (direct synthesis) or the chiral co-ligands to control the stereochemistry at the metal centers. Below is the detail of these strategies.
In order to synthesize chiral MOFs or COFs for specific applications the term “design synthesis” is usually used, according to which the resulting frameworks components are first carefully designed to utilize them for framework construction. In addition during the synthesis, environment and conditions are also carefully controlled for the efficient construction of solid materials. In general a number of different synthesis methods have been developed and reported so far, which include solvothermal synthesis, ionothermal, microwave assisted synthesis, electrochemical synthesis, mechanochemical synthesis and sonochemical synthesis [14, 15].
Most of the chiral materials are being synthesized using design synthesis by direct or bottom up strategy, in which the homochirality in the resulting framework comes from the starting materials. Such type of the synthesis is also known as “chirality conversion process” [16]. In 2015 Jian Zhang and coworkers synthesized a homochiral MOF “FIR-28” (Fujian Institute of Research) an 8-fold interpenetrating srs-type MOF based on (Figure 1). The synthesis was based on direct solvothermal synthesis using the ligand of interest and metal salt, Zn(NO3)26H2O [17].
Structure of the H3TPA ligand, (a) single framework in FIR-28, (b) P-helix, (c) M-helix, (d) 3-connected srs network in FIR-28, and (e) 8-fold interpenetrating framework of FIR-28.
A Boc-protected proline based homochiral MOF DUT-32-NHProBoc was synthesized by Stefan Kaskel group in 2014. The direct synthesis using proline based linker was not successful, so their group functionalized the ditopic linker (4,4′-biphenyldicarboxylic acid) with a chiral BOC-protected proline functionality (NHProBoc group) in three steps. They used two ligands a tritopic 4,4′,4″-[benzene-1,3,5-triyltris (carbonylimino)] trisbenzoate (btcb3) and ditopic 4,4-biphenyldicarboxylate (bpdc2) with Zn(NO3)2·4H2O salt by direct synthesis (Figure 2) [18]. Using bottom-up approach, in 2016 a series of thermally stable chiral COFs, CTpPa-1, CTpPa-2 and CTpBD were successfully synthesized that exhibit a two-dimensional eclipsed layered sheet structure (Figure 3) [19].
(a) Linker used for the synthesis of DUT-32-NHProBoc, (b) crystal structure of DUT-32-NHProBoc and (c) simplified representation of four pore types highlighting bordering chiral ligands L2.
(a) Synthesis of CTp through the esterification of Tp and (+)-Ac-L-Ta, (b) synthesis of chiral COFs through the condensation of CTp and Pa-RR1, (c) graphical view of CTpPa-1, (d) eclipsed structure of CTpPa-1. C, gray; N, blue, O, red; H omitted for clarity.
Wei Wang and coworkers used a facile strategy for the direct construction of chiral functionalized COFs, LZU-72 and LZU-76 using chiral pyrrolidine-containing building blocks. They used 4,4′-(1H-benzo [d] imidazole-4, 7-diyl) dianiline as a rigid scaffold in order to attach chiral moieties. As a result chiral pyrrolidine-embedded building block (S)-4,4′-(-(pyrrolidin-2-yl)-1H-benzo [d] imidazole-4,7-diyl) dianiline was accordingly synthesized and used to successfully construct the above mentioned chiral COFs [20].
In 2005 Lin and coworkers synthesized a series of catalytically active chiral MOFs by designing a variety of chiral pyridyl, carboxylates and phosphonate bridging ligands with orthogonal functional groups using readily available chiral 1,1′-bi-2-naphthol (BINOL) [21]. While in 2012 their group synthesized a highly fluorescent chiral MOF from 1,1-bi-2-naphthol (BINOL) based chiral tetracarboxylate bridging ligand and a cadmium carboxylate infinite chain secondary building unit [22].
In 2008 Jian Zhang et al. described unusual integrated homochirality features in six 3D MOFs containing enantiopure building blocks embedded in intrinsically chiral topological quartz net. Direct synthesis using solvothermal method was used to construct these MOF materials from economically cheap ligands; D or L camphoric acid and divalent or trivalent metal ions in the presence of achiral template cations or molecules. Single crystal analysis revealed that all six MOFs have three homochiral features: 3D intrinsically homochiral net (quartz, quartz dual, srs net), enantiopure molecular chirality and homohelicity. It is noteworthy that chirality of molecular building blocks controls the absolute helicity in each case [23]. In 2014 this group further developed a low-cost homochiral MOF platform which was based on the inexpensive
In 2014 two chiral micro- and mesoporous MOFs were synthesized using stepwise assembly of triple-stranded heptametallic helicates with six carboxylic acid groups. The mesoporous framework proved to be an efficient recyclable heterogeneous catalyst when encapsulated with an enantiopure organic amine catalyst. The organocatalyst-loaded framework catalyze the asymmetric direct aldol reactions with significantly in proved stereo-selectivity in comparison to the homogenous organocatalyst [25]. In the past few years, the UiO family of MOFs with linear dicarboxylate organic linkers and Zr6(μ3-O)4(μ3-OH)4 SBUs has particularly been synthesized by direct synthesis method. These MOFs are an ideal platform to design highly efficient MOF catalysts because of their stability in harsh reaction conditions and broad range of solvents [26, 27].
Different chiral ligands have been used for the direct synthesis of chiral microporous frameworks, some of them are given in Figure 4.
Different chiral ligands used to construct chiral porous materials.
In order to prepare a chiral crystalline material from achiral building units different strategies have been applied including, chiral templating, chiral induction, solvent effects, and chiral additive effects. The key feature in all of these processes is the transfer of chiral information from a chiral species to the nucleus of growing crystallite. For successful crystallization of chiral frameworks, such information transfer needs to be very specific, and probably requires quite strong directional bonding to the substrate crystal. That’s the reason templating is rather a disappointing method of forming chiral crystals from achiral building blocks because it might cause framework collapse once the template is thermally removed [5].
In this chapter we will discuss some of the techniques that have been used by different research groups to synthesize chiral MOFs and COFs. One of the important aspects that should be kept in consideration is that the bulk sample must be homochiral. Different bulk measurement techniques have been developed and used so for, such as circular dichroism (CD) spectra, VCD spectrum, or multiple single-crystal for checking the homochirality of the bulk material [28, 29].
In comparison to the direct synthesis, a little progress has been achieved in asymmetric crystallization of enantiopure or enantioenriched materials through chiral induction using achiral precursors. There is great deal of similarity between chiral induction by enantiopure additives and asymmetric catalysts used by organic chemists to synthesize chiral molecules. Although there is no direct proofs of how a chiral solvent or a chiral additive plays its role of induction, recent examples of chiral induction by additive/solvents (Table 1) suggest that chemical bonding interaction between additives and cationic metal sites might be the reasons of induced chirality [5].
Formula of chiral material | (BMIM)2[Ni(HTMA)2(H2O)2 | [(CH3)2NH2][In(thb)2]·(DMF)x | Mn3(HCOO4(adc) | NaZnPO4·H2O |
---|---|---|---|---|
Name or zeolite structure code | SIMOF-1 (St Andrews ionothermal MOF-1) | ATF-1P and ATF-1M (ATF, anionic tetrahedral framework) | Mn-1D and Mn-1L | CZP (chiral zeolite phosphate) |
Key structural features | Anionic MOF with ionic liquid cation as template/guest | Anionic MOF with 2-fold diamond topology. | Neutral MOF with honeycomb channels | Anionic zeolite-type inorganic framework |
Chiral symmetry | P43212 and P41212 | P4122 and P4322 | P3121 and P3221 | P6122 and P6522 |
Chiral induction agents (CIA) | Chiral ionic liquid BMIM | (−)-Cinchonidine for P4122 or (+)-cinchonine for P4322 | (−)-Uridine 5′-phosphate (ump) for P6122 | |
What if CIA is not used? | Formation of achiral material with different structure (SIMOF-2) | Racemic twins | A different crystal structure, Mn (adc) | Racemic |
Solvent | BMIM | DMF or DEF | Mixed DMF and ethanol | Water |
Crystallization temperature | 110°C | 120°C | 120°C | 80°C |
A summary of asymmetric crystallization induced by chiral additives or solvents.
A more recent discovery of chiral induction by Zhang et al. supports the above proposed mechanism that the chiral induction is likely to involve the coordinate bonding between framework metal sites and chiral additives. In 2010 their group explored the enantioselective effect of inexpensive asymmetric molecular catalysts such as enantiopure organic acid (camphoric acid) and naturally occurring amino acid (glutamic acid) for asymmetric crystallization of 3D crystalline porous materials from achiral building units. In this case, the absolute chirality of chiral MOF [Mn3(HCOOH)4]2+ is determined by the chirality of
(a) [Mn(adc)]n chain based on achiral adc ligand with μ4 coordination; (b) porous [Mn3(HCOOH)4]n2+ channel based on inorganic Mn─O─Mn connectivity; (c) two types of enantiopure catalysts used for the synthesis and chiral induction of 1D; the direction of arrows show the possible mechanism of chiral induction. d-camphoric acid initially controls the absolute chirality of [Mn3(HCOOH)4]n2+ frameworks but is later displaced by adc. (d) 3D hybrid framework of 1D, showing the achiral [Mn(adc)]n chains attached to the wall of the nanosized channels.
Illustration of four crystallization processes showing that camphorate ligand not only controls the absolute chirality of crystals, but also enables and catalyzes the growth of chiral crystals.
An early example of chiral induction of porous solids by additives involves the use of chiral alkaloids to induce the absolute chirality of a microporous indium dicarboxylate. In 2008 a series of MOFs, ATF-1, ATF-1P or ATF-1M; (ATF anionic tetrahedral framework; P and M denotes handedness) were synthesized using solvothermal reactions of In(NO3)3·xH2O and ligand H2thb with (or without) cinchonidine or cinchonine in two different solvents (1, DMF; 2, DEF) instead of using chiral solvents, chiral spectator solutes (−)-cinchonidine or (+)-cinchonidine were used to induce the chirality (Figure 6) [16].
Schematic illustration of the generation of conglomerate (ATF-1) or bulk homochirality (ATF-1P and ATF-1M) induced by (−)-cinchonidine or (+)-cinchonine from the basic 4-connected building block with achiral precursors.
In 2005 a 2D layered coordination polymer Co(PDC)·(H2O)2 have been developed, which was comprised of two helical chains using an achiral ligand, pyridine-2,5-dicarboxylic acid (H2PDC). Its synthesis did not involve any chiral reactant or solvent or any other auxiliary agent. Surprisingly, the resultant crystals were not racemic as investigated by the observation of strong signals in vibrational circular dichroism (VCD) spectra. Chirality might come from spatial organization of achiral building blocks in crystalline frameworks [31].
Recently a series of nine chiral 2D-COFs have been synthesized using (R)- or (S)-1-PEA as a chirality inducing catalyst, through imine condensations of Tp with diamine or triamine linkers, as indicated in Figure 7. Among these COFs, CCOF-TpTab exhibited greater enantioselectivity towards chiral carbohydrates in fluorescent quenching. After post-synthetic modification of the enaminone groups with Cu(II) ions, the solid was converted in to a recyclable heterogeneous catalyst which can be used for asymmetric Henry reaction of nitroalkane with aldehydes [32].
Schematic demonstration of the synthesis of CCOFs. These CCOFs are synthesized from achiral precursors by chiral catalytic induction.
MOFs and COFs can be modified to improve their catalytic properties through covalent and coordinate covalent PSM. A variety of active and chiral functional groups can be tethered to metal nodes and organic ligands to convert MOFs and COFs in to catalytically active materials. Through PSM, a single MOF can be modified with several combinations of functional groups and thereby tested as a catalyst for different reactions [33].
Kimoon Kim and coworkers reported the first example of modifying an achiral MOF “MIL-101(Cr)”, built from Cr3+ trimer SBUs and BDC [34] in to an active chiral catalyst. They modified MIL-101 (Cr) in to two chiral MOFs CMIL-1 and CMIL-2, by replacing the coordinated solvent with
In 2014 the first example of pore surface engineering of stable imine linked COF was reported. Pore surface engineering allows a general principle for designing catalytic COFs and molecular design of COF skeletons by controlling the density and composition of the functional groups on the pore walls. Mesoporous imine-linked porphyrin COF [HC☰C]-X-H2P-COF was used as a scaffold. Using the click reaction of this COF with pyrrolidine azide in the presence of a CuI catalyst in toluene-tert-butanol at 25°C yielded the corresponding [Pyr] X-H2P-COFs (as illustrated in Figure 8). Pyrrolidine derivatives are renowned organocatalysts for Michael addition reaction [36, 37]. Engineering pyrrolidine units onto the pore walls generates aqueous organocatalytic COFs with a number of striking catalytic features, including enhanced activity, good recyclability, and high capability to perform transformation. The catalytic activity depends upon the density of the active sites on the pore walls [38].
The general strategy for the pore surface engineering of imine-linked COFs by a condensation reaction and click chemistries (the case for X = 50 was exemplified).
Recently Yong Cui and coworkers synthesized two isostructural 2D Zn (salen)-based CCOFs (chiral covalent organic frameworks) by co-condensation of chiral 1,2-diaminocyclohexane and trisalicylaldehydes alkyl groups. Chiral salen ligands such as (R,R)-1,2-cyclohexanediamino-N,N′-bis-(tert-butyl-salicylidene) are well-known ligands for asymmetric catalysis [39]. By post-synthetic metal exchange, the framework of these CCOFs can be modified for asymmetric catalysis. Their group postsynthetically exchanged Zn2+ ions with Cr, Fe, Mn and Co, and analyzed the improvement of efficiency in asymmetric catalysis, stereoselectivities and recyclability of catalyst [40].
Like molecular homogenous catalysts, MOFs allow for almost the same level of structural rectification, while their large surface area, permanent porosity, and heterogeneous nature facilitate rapid purification and better catalytic activity [26, 41, 42, 43, 44]. Among all the chiral MOFs with improved stereo-selective catalysis reported so far, the most privileged examples are all directly crystallized from efficient chiral ligands, including, BINOL- and salen-based derivatives, but it is challenging to synthesize and grow large single crystals for structural elucidation and to prepare highly stereo-selective catalysts comparable or even extraordinary to their homogeneous counterparts [45, 46, 47, 48]. Solvent-assisted linker exchange (SALE) have been proved to be incredibly effective for the synthesis of MOFs that are difficult to approach de-novo [33, 49, 50, 51, 52, 53]. According to this strategy crystals of a template MOF are placed in the excess solution of secondary linker, as the reaction proceeds the new linker replaces the original MOF linkers while the daughter framework retains the original MOF topology. In addition to the incorporation of desired linker, SALE also proved to be an effective method to incorporate many interesting properties in to the framework like, introduction of catalytically active moieties, incorporation of free carboxylic acid groups by functionalizing defect sites, and enhance proton conductivity as well as photochemical H2 production. In 2015 Yong Cui and coworkers employed a genius approach of synthesizing chiral MOFs using direct synthesis and then by employing SALE they post-synthetically modified one of the chiral VO salen based MOF-2 in to mixed linker salen based MOF-2Cr by exposing MOF-2 to a DMF/MeOH solution of [CrL2Cl] at 60°C for 8 h which led to the partial replacement of units with [Cr(salen)Cl] (2Cr) [12]. Chiral vanadium and chromium salen complexes are famous for their asymmetric catalysis of different types of organic reactions [54, 55, 56].
Homo-chiral microporous materials proved to be not only promising candidates for heterogeneous asymmetric catalysis but also enantioselective adsorbents or separators for the production of optically active organic compounds. Therefore the exploration of homo-chiral microporous materials towards the adsorption and diffusion of enantiomeric molecules is essential and important to promote these materials for chiral resolution [1]. Properly designed microporous MOFs and COFs with uniform, periodically aligned active sites have shown great potential in catalyzing shape-, size-, chemo-, region-, and stereo-selective organic transformations as well as fabricating optically active hybrid materials and devices.
In 2000 Kim el al. reported the synthesis of a homochiral metal organic framework (D-POST-1) that allows the enantioselective inclusion of metal complexes in its pores and catalyzes a trans-esterification reaction in an enantioselective manner. D-POSt-1 built up by the oxo-bridged tri-nuclear metal carboxylates clusters and enantiopure chiral ligand derived from
Trans-esterification in the presence of POST-1.
Xiong et al. prepared a new enantiopure chiral ligand HQA-(6′-methoxy-(8S,9R)-cinchonan-9-ol-3-carboxylic acid) from quinine, “an off-the-shelf antimalarial alkaloid” and utilized it to synthesize a homo-chiral MOF [Cd(QA)2]. The enantioselective separation activity of this MOF was investigated by solvothermal reaction of the powder sample of Cd(QA)2 in the racemic 2-butanol solution at 100°C for 3 days. As a result, a crystalline sample of ((S)-2butanol)@[Cd(QA)2 was analyzed by the single-crystal X-ray diffraction that revealed the inclusion of (S)-2-butanol in to the chiral cavity. The ee value of 2-butanol desorbed from ((S)-2butanol)@[Cd(QA)2 was assessed to be approximately 98.2%. When larger racemic 2-methyl-1-butanol was used, the ee value of (S)-2-methyl-1-butanol obtained was reduced to only 8.2%. Such differences in selectivity for chiral molecules of different size suggest that an appropriate match between pore dimension and the size of chiral guest is the crucial factor for enantioselective adsorption [58].
Although several porous materials such as activated carbon, silica gel, zeolites, and various polymer resins proved to be useful stationary phases in gas chromatography, liquid chromatography and electro-chromatography, MOFs are far less explored for these applications. In 2007, Fedin and Bryliakov et al. reported the first example of utilizing a homochiral 3D porous Zn-MOF “Zn2(bdc)(L-lac)(DMF)” in chiral liquid chromatography (LC) column for resolution of racemic mixtures of chiral alkyl aryl sulfoxides [59, 60].
In 2006 Rosseinsky and coworkers synthesized microporous chiral MOF [Ni2(L-asp)2(bipy) using cheap and readily available amino acid (aspartic acid). Nine chiral diols, having very close functionalities were enantioselectively adsorbed on this chiral MOF at 278 K, which showed that a good match of size and shape between small chiral guest and chiral pore of the homochiral framework is the decisive factor for chiral resolution application. 2-Methyl-2,4-pentanediol demonstrated the highest enantiomeric excess of 53.7%, attributable that both hydroxyl groups of (S)-2-methyl-2,4-pentanediol are involved in hydrogen bonding within the chiral channels [61].
Nowadays membrane separation offers great potential owing to the outstanding prevalence over the traditional methods, such as low-energy consumption, large processing capacity, and a continuous mode of operation. Due to their well-defined porosity and stability, zeolites and mesoporous MOF membranes have attracted a huge interest in engineering applications, such as gas and liquid separations, membrane reactors and chemical sensors. However, it’s still very challenging to synthesize these materials with required chirality, which is the core for chiral separation.
In 2012, first homochiral MOF membrane ‘Zn-BLD’ (Zn2(bdc)(L-lac)(dmf) was fabricated on a porous zinc oxide substrate through a reactive seeding technique. This membrane was used for the enantioselective separation of important chiral compounds especially drug intermediates which was a new step towards the potential development of sustainable and highly efficient chiral separation technique. Intriguingly, homochiral MOF membranes are expected to possess high enantioselectivity as a result of their open chiral channels or cavities and high permeation flux due to high porosity and low mass transfer resistance. Zn-BLD exhibits enantioselective separation of racemic MPSs with preferential adsorption ability to (S)-(MPS over (R)-MPS. At the feed concentration of 5 mmol L−1, an ee value of 33.0% for R-MPS over S-MPS was obtained which was attributed to the different interactions of the two enantiomers with the Zn-BLD inner pores. Such a highly enantioselective separation approach brings advanced materials science to the forefront of a major society need [62].
In 2012, a highly sensitive chiral MOF sensor ‘1’ with greatly enhanced enantioselectivity towards chiral amino alcohols in fluorescent quenching was built from 1,1′-bi-2-naphthol (BINOL) derived chiral tetracarboxylate bridging ligand and a cadmium carboxylate infinite chain secondary building unit. 1 shows higher sensitivity towards chiral amino acids with unprecedentedly high SV constants of up to 31,200 M−1 and an impressive enantioselectivity, with an enantiomeric quenching ratio [KSV(S)/ KSV(R)] of 3.12 for 2-amino-3-methyl-1-butanol. Conformational rigidity of BINOL as well as pre-concentration of the quencher inside the cavities of 1 are the main factors for greatly enhanced detection sensitivity. The confinement effect of MOF cavities for chiral discrimination of analyte and the conformational rigidity of the sensing sites can be utilized to design new MOF materials for future sensing devices [22].
A vast majority of MOFs are prepared by using modular assembly, in which organic struts and inorganic joints are connected in three dimensional networks. Such type of modular assemblies results in the formation of two types of domains in the frameworks, (i) sorting domain [63], whereby the pore apertures act as sieves based on size- and shape-selectivity or (ii) a coverage domain [64] wherein the internal pore surfaces interact non-specifically with guest molecules as a consequence of non-covalent binding forces. In 2010 team of Omar M. Yaghi and J. Fraser Stoddart employed a novel approach known as designer approach, to design active domains [65] with in the MOFs. By using the designer approach their team has successfully constructed new type of distribution domain, the active domains, where an ordered distribution of guests throughout the MOF is maintained by highly specific stereoelectronic control and these active domains are capable of stereoselective molecular recognition. In their reported work, they incorporated the dilocular (two chiral elements) struts (SS)-2 and (RR)-2 containing optically active dilocular bis-binaphthyl [22] crown-6, into (SS)-MOF-1020 and (RR)-MOF-1020 respectively. Such a precise placement of optically active organic struts inside MOF, pave the way well for the advancement of a range of exquisitely engineered chiral stationary phases for carrying out the separation of enantiomers by HPLC [66].
MOFs serve as heterogeneous asymmetric catalysts and their role in asymmetric catalysis was first demonstrated by Fujita et al. in 1994 who synthesized a crystalline porous coordination polymer catalyst for cyanosilylation of aldehydes [67]. Afterwards Aoyama and co-workers developed Ti complex based amorphous microporous solid catalyst for stereoselective Diels Alder reaction [68]. Although it was proposed that the incorporation of catalytically active units in the MOFs can promote the field of asymmetric catalysis but there was no proper report on asymmetric catalysis promoted by structurally well-characterized metal organic systems until 2000. The first homochiral MOF, “POST-1” exhibiting catalytic activity for an asymmetric chemical reaction was reported by Kim and coworkers [57]. Lin and coworkers in 2001 reported the first asymmetric catalysis promoted by metal ions at the nodes of framework [69]. In 2005 their group also adopted a systematic strategy to use privileged chiral ligands, such as BINOL for chiral MOFs used in catalytic asymmetric transformations [21]. In short there are many groups who have been working on the development of homochiral MOF based catalysts since 2005 to present noticeably Lin and coworkers, Hupp and Nguyen et al. and Kim and coworkers [47, 63, 68]. There are some general requirements to be fulfilled by homochiral MOF based catalysts, including close proximity of catalytic centers and chiral induction sites, large accessible pores/channels that allow facile diffusion of substrates and products, and ability to maintain structural integrity during the catalytic process. Due to stringent requirements for successful applications in asymmetric heterogeneous catalysis, the MOF based chiral catalysts are still scarce in literature and this area needs a lot of development [41].
Although it’s difficult to quote all the examples of MOF based heterogeneous catalysts since their discovery in 2000 until now, but we will try to discuss some of the recent examples in this chapter.
Chiral manganese salen complexes are highly effective asymmetric catalysts for olefin epoxidation. In 2006, Albrecht-Schmitt and coworkers synthesized a paddlewheel-stabilized MOF using Mn salen complex and H2bpdc ligand. The MOF-based catalyst confers higher stability, easier separation, recyclability, and substrate size selectivity, as compared to free catalyst [47].
In 2010 Tanaka et al. prepared Cu paddle wheel based chiral MOF (R)-3 and employed this MOF as a catalyst for the kinetic resolution of styrene oxide in the presence of different alcohols. They observed that the kinetic resolution was very sensitive to the structure of alcohols, with MeOH showing the highest conversion and enantioselectivity while bulkier alcohols e.g., EtOH, i-PrOH and t-BuOH, the conversion as well as enantioselectivity was decreased. They proposed a suitable mechanism and explained the reason for the high activity of (R)-3 in the presence of methanol. According to their analysis in the presence of methanol, evacuated MOF is transformed in to 2D in which the substrate is accessible to the Cu active site through diffusion. A pronounced color change was observed from black to green in MeOH during the transformation [45].
Network structure dependent catalytic activity of two chiral Cd MOFs was demonstrated by Lin and coworkers in 2007. They synthesized two Cd MOFs, 1 and 2, using two different salts Cd(NO3)·4H2O2 and Cd(ClO4)·6H2O2 with (R)-6,6′-dichloro-2,2′-dihydroxy-1,1′-binaphthyl-4,4′-bipyridine respectively. They tried to generate heterogeneous asymmetric catalysts by activating Lewis acidic metal centers (namely, Ti(OiPr)4) with the chiral dihydroxy groups that are present as the orthogonal secondary functionalities in the porous solids 1 and 2. Treatment of 1 with Ti(OiPr)4 led to an active catalyst (1.Ti) that efficiently catalyzes the addition of diethylzinc to aromatic aldehydes while mixture of 2 and Ti(OiPr)4 under similar conditions did not show the catalytic activity. The absence of catalytic activity with the 2/Ti(OiPr)4 system is a consequence of the steric hindrance around the chiral dihydroxy groups which prevents the substitution of two isopropoxide groups by the binolate functionality [70]. Lin group made a number of remarkable efforts in developing MOF based active catalysts. In 2010 their group demonstrated a systematic design of eight mesoporous isoreticular CMOFs using copper paddle-wheels and 1′-1,1′-bi-2-naphthol with similar structures but channels of different sizes. By using post-synthetic functionalization with Ti(OiPr)4 they generated chiral Lewis acid catalyst which proved to be highly efficient for conversion of aromatic aldehydes in to chiral secondary alcohols, through addition of alkylzinc or diethylzinc. By slight alteration in BINOL based likers, the size of the channels were modified, which alters the diffusion rates of the organic substrates [48].
Yong Cui and coworkers synthesized a homochiral MOF using an enantiopure 2,2′-dihydroxy-1,1′-biphenyl ligand with Zn(NO3)2·6H2O through solvothermal reaction. Through one proton exchange of the dihydroxyl group with Li(I) ions, the framework proved to be a highly efficient and recyclable heterogeneous catalyst for asymmetric cyanation of aldehydes with up to >99% ee [44].
COFs are among some of the emerging classes of advanced materials which have been greatly seeking the attention of not only chemists but also material scientists. Since the seminal work of Yaghi and coworkers, this class of materials has been through a great deal of progress to serve them for industrial applications. Among its various other applications the most important are their use in enantioselective separations and catalysis. So far, only few chiral COFs have been successfully constructed due to their challenging synthesis and the key bottleneck of creating chiral COFs is the inherent discrepancy between the symmetry for crystalline structures and asymmetry for chiral functionalities. According to the context of this chapter we will briefly try to highlight some examples of CCOFs which played an efficient role in chiral separations and asymmetric catalysis.
Owing to the large surface area, permanent porosity, high solvent and thermal stability, COFs are considered as good candidates to be used for enantiomeric separation of small molecules, especially of biological or pharmacological interest. Yan and coworkers in 2016 synthesized three CCOFs namely, CTpPa-1, CTpPa-2 and CTpBD and then using in situ growth, they fabricated chiral COF bound capillary columns. These chiral COF capillary columns displayed high resolution for the separation of (±)-1-phenylethanol, (±)-1-phenyl-1-propanol, (±)-methyl lactate, and (±)-limonene, which can be efficiently separated within 5 min under excellent repeatability and reproducibility [19].
In 2018 the first chiral 3D COF was constructed by imine condensation of a 2-fold symmetric TADDOL-derived tetraldehyde with a tetrahedral tetra (4-anilyl) methane and transformed in to amide linked COF after post-synthetic oxidation of imine linkages. Both the imine linked COF as well a post-synthetically modified imide linked COF, served as highly reproducible chiral stationary phases for HPLC [71].
COF is an emerging field of material chemistry and needs a lot of development. The ordered nano-channels and periodic layers in COFs make these materials sustainable open catalytic nano-reactors, but their low stability has prohibited their practical application. Among various other groups working on development of CCOFs, Donglin Jiang and his group has achieved a remarkable progress in this regard. In 2015 they synthesized a mesoporous imine based COF “TPB-DMTP-COF” with improved crystallinity and high chemical and thermal stability, by the incorporation of methoxy groups in to the pore walls. They post-synthetically modified this achiral COF in to two distinct CCOFs by engineering the channel walls with chiral centers and organocatalytic species. The resulting crystalline, metal free catalysts presented activity, enantioselectivity, recyclability and environmental benevolence, a set of characteristics that has remained challenging to engineer in heterogeneous catalysis [72].
This chapter summarizes the recent advances in the development of chiral microporous materials, with special emphasis to metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). We discussed some of the synthetic strategies in details and highlighted the current status of chiral microporous materials in enantioselective separation and asymmetric catalysis. Since there is a lot of development needed to be done in this area, as it can open up new doors to the synthesis of advanced green energy materials and catalysis.
metal organic framework covalent organic framework chiral covalent organic frameworks Fujian institute of research tris(4-carboxylphenylduryl)amine tert-butyloxycarbonyl Dresden University of Technology secondary building units adamantane-1,3-dicarboxylic acid phenyl-ethylamine 1,3,5-triformylphloroglucinol 1,3,5-tri(4-aminophenyl)benzene postsynthetic modification methyl phenyl sulfoxides 1,1′-bi-2-naphthol
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