Investigation of four roof-shaped host compounds for their separation potential of mixtures of guest Isomers and related compounds
- Authors: Senekal, Ulrich
- Date: 2024-04
- Subjects: Grignard reagents , Optical isomers -- Analysis , Supramolecular chemistry
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/64368 , vital:73684
- Description: The inclusion ability of four roof-shaped host compounds, namely trans-9,10-dihydro-9,10- ethanoanthracene-11,12-dicarboxylic acid (H1), dimethyl trans-9,10-dihydro-9,10- ethanoanthracene-11,12-dicarboxylate (H2), trans-α,α,α’,α’-tetraphenyl-9,10-dihydro-9,10- ethanoanthracene-11,12-dimethanol (H3) and trans-α,α,α’,α’-tetrakis(4-chlorophenyl)-9,10- dihydro-9,10-ethanoanthracene-11,12-dimethanol (H4), were investigated when presented with numerous guest series (eight in number), including the xylene isomers and ethylbenzene, pyridine and the methylpyridine isomers, structurally related toluene, ethylbenzene and cumene, the dichlorobenzenes, six-membered heterocyclic ring compounds (dioxane, morpholine, piperidine and pyridine), anisole and the methylanisole isomers, anisole and the bromoanisole guests, and phenol and the methoxyphenol isomers. The four host compounds were synthesized via Diels-Alder (H1), esterification (H2) and Grignard addition (H3 and H4) reactions, producing yields of product of up to 93%. The yields for the Grignard reactions were lower, 54 and 37%, for the corresponding procedures using phenylmagnesium bromide or 4-chlorophenylmagnesium bromide. Computational molecular modelling studies were conducted on all four host compounds, and the resultant molecular geometries compared with the apohost (guest-free) crystal structures, when available. The geometries of the lowest energy conformers were in close correlation with the observed host structures as obtained from the apohost crystal structures (unfortunately, H3 and H4 were not able to form adequate quality crystals for SCXRD analyses). Interestingly, H1–H4 displayed intramolecular non-classical C–H∙∙∙O hydrogen bonds, while only H1 and H2 demonstrated intermolecular interactions of this type. H3 and H4 assumed one of two forms depending on the guest that was employed: the “active” form presented a strong intramolecular O–H∙∙∙O hydrogen bond, while the “inactive” form possessed weak π∙∙∙π and O–H∙∙∙π interactions. All of the host compounds were subjected to crystallization experiments from each of the guest species, as well as from mixtures of guests from each series (the guest competition experiments), where 1H-, 13C-NMR spectroscopy, GC-MS and/or GC-FID were used to analyse any resultant solids formed, as applicable. Single crystal X-ray diffraction (SCXRD) experiments were carried out on each single solvent complex produced in this work, where the crystal quality was suitable, while thermal analyses were also employed on these to determine their relative thermal stabilities. During the single-guest crystallization experiments, H4 was found to be remarkable in its inclusion ability, forming complexes with all but p-dichlorobenzene, typically with a 1:1 host:guest (H:G) ratio. H1 was more selective in its inclusion behaviour, not enclathrating cumene, 3-bromoanisole, phenol or the three methoxyphenol isomers (favouring 1:1 or 2:1 H:G ratios where complexation was successful). Interestingly, H1 formed salts when presented with 2- and 3-methylpyridine, and morpholine and piperidine. H2 and H3 were less remarkable in their inclusion ability, furnishing apohost crystals or gels in some experiments (typically a 3:1 H:G ratio was favoured for both when complexation occurred). Of the four roof-shaped host compounds, H1 and H4 displayed enhanced selectivities for certain guest species, showing near-complete affinity for a specific guest compound when presented with a guest mixture. H1 was able to include 100.0 and 98.8% p-dichlorobenzene (p-DCB) (from m-DCB/p-DCB and o-DCB/p-DCB mixtures), 96.6 and 93.6% p-xylene (p-Xy) (from m-Xy/p-Xy and o-Xy/p-Xy), 99.3% 4-methylanisole (4-MA) (from 2-MA/4-MA) and 97.1% 4-bromoanisole (4-BA) (from ANI/2-BA/3-BA/4-BA, where ANI is anisole). Host compound H4 was able to include ≈ 90% of selected meta-substituted guests, while H2 and H3 demonstrated moderate preferences for the guest compounds employed in this work (< 60%). It was concluded that some xylene guest mixtures may be purified using all but H2, whereas only H1 and H2 showed potential in separating the pyridines. All but H2 may also be employed in the separation of selected dichlorobenzene mixtures, while H2 showed potential for the separation of the six-membered heterocyclic guest compounds (dioxane, morpholine, piperidine and pyridine), were these ever required to be separated. Both H1 and H4 exhibited an overwhelming affinity for the methyl- and bromoanisole guest compounds, and this work has shown that these are likely host candidates for the purification of a variety of these guest mixtures through supramolecular strategies. SCXRD analyses showed that H1 experienced intermolecular host···host hydrogen bonding interactions between the carboxylic acid functional groups, while H2 typically demonstrated intermolecular non-classical hydrogen bonds in its complexes, forming sheets of host molecules along the c-axis. H4 preferred the “inactive” form whereas H3 assumed either an “active” or “inactive“ form. Various host···guest interactions such as π∙∙∙π, C–H∙∙∙π, C–O∙∙∙π, hydrogen bonding and other short contacts were responsible for guest retention in the crystal structures. Thermal analyses were conducted on all of the successfully formed complexes. Ton (the guest release onset temperature) and Tp (the temperature at which the guest release was most rapid) were recorded, when possible, while the mass losses associated with the guest release event were compared with those mass losses expected, in most cases. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Senekal, Ulrich
- Date: 2024-04
- Subjects: Grignard reagents , Optical isomers -- Analysis , Supramolecular chemistry
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/64368 , vital:73684
- Description: The inclusion ability of four roof-shaped host compounds, namely trans-9,10-dihydro-9,10- ethanoanthracene-11,12-dicarboxylic acid (H1), dimethyl trans-9,10-dihydro-9,10- ethanoanthracene-11,12-dicarboxylate (H2), trans-α,α,α’,α’-tetraphenyl-9,10-dihydro-9,10- ethanoanthracene-11,12-dimethanol (H3) and trans-α,α,α’,α’-tetrakis(4-chlorophenyl)-9,10- dihydro-9,10-ethanoanthracene-11,12-dimethanol (H4), were investigated when presented with numerous guest series (eight in number), including the xylene isomers and ethylbenzene, pyridine and the methylpyridine isomers, structurally related toluene, ethylbenzene and cumene, the dichlorobenzenes, six-membered heterocyclic ring compounds (dioxane, morpholine, piperidine and pyridine), anisole and the methylanisole isomers, anisole and the bromoanisole guests, and phenol and the methoxyphenol isomers. The four host compounds were synthesized via Diels-Alder (H1), esterification (H2) and Grignard addition (H3 and H4) reactions, producing yields of product of up to 93%. The yields for the Grignard reactions were lower, 54 and 37%, for the corresponding procedures using phenylmagnesium bromide or 4-chlorophenylmagnesium bromide. Computational molecular modelling studies were conducted on all four host compounds, and the resultant molecular geometries compared with the apohost (guest-free) crystal structures, when available. The geometries of the lowest energy conformers were in close correlation with the observed host structures as obtained from the apohost crystal structures (unfortunately, H3 and H4 were not able to form adequate quality crystals for SCXRD analyses). Interestingly, H1–H4 displayed intramolecular non-classical C–H∙∙∙O hydrogen bonds, while only H1 and H2 demonstrated intermolecular interactions of this type. H3 and H4 assumed one of two forms depending on the guest that was employed: the “active” form presented a strong intramolecular O–H∙∙∙O hydrogen bond, while the “inactive” form possessed weak π∙∙∙π and O–H∙∙∙π interactions. All of the host compounds were subjected to crystallization experiments from each of the guest species, as well as from mixtures of guests from each series (the guest competition experiments), where 1H-, 13C-NMR spectroscopy, GC-MS and/or GC-FID were used to analyse any resultant solids formed, as applicable. Single crystal X-ray diffraction (SCXRD) experiments were carried out on each single solvent complex produced in this work, where the crystal quality was suitable, while thermal analyses were also employed on these to determine their relative thermal stabilities. During the single-guest crystallization experiments, H4 was found to be remarkable in its inclusion ability, forming complexes with all but p-dichlorobenzene, typically with a 1:1 host:guest (H:G) ratio. H1 was more selective in its inclusion behaviour, not enclathrating cumene, 3-bromoanisole, phenol or the three methoxyphenol isomers (favouring 1:1 or 2:1 H:G ratios where complexation was successful). Interestingly, H1 formed salts when presented with 2- and 3-methylpyridine, and morpholine and piperidine. H2 and H3 were less remarkable in their inclusion ability, furnishing apohost crystals or gels in some experiments (typically a 3:1 H:G ratio was favoured for both when complexation occurred). Of the four roof-shaped host compounds, H1 and H4 displayed enhanced selectivities for certain guest species, showing near-complete affinity for a specific guest compound when presented with a guest mixture. H1 was able to include 100.0 and 98.8% p-dichlorobenzene (p-DCB) (from m-DCB/p-DCB and o-DCB/p-DCB mixtures), 96.6 and 93.6% p-xylene (p-Xy) (from m-Xy/p-Xy and o-Xy/p-Xy), 99.3% 4-methylanisole (4-MA) (from 2-MA/4-MA) and 97.1% 4-bromoanisole (4-BA) (from ANI/2-BA/3-BA/4-BA, where ANI is anisole). Host compound H4 was able to include ≈ 90% of selected meta-substituted guests, while H2 and H3 demonstrated moderate preferences for the guest compounds employed in this work (< 60%). It was concluded that some xylene guest mixtures may be purified using all but H2, whereas only H1 and H2 showed potential in separating the pyridines. All but H2 may also be employed in the separation of selected dichlorobenzene mixtures, while H2 showed potential for the separation of the six-membered heterocyclic guest compounds (dioxane, morpholine, piperidine and pyridine), were these ever required to be separated. Both H1 and H4 exhibited an overwhelming affinity for the methyl- and bromoanisole guest compounds, and this work has shown that these are likely host candidates for the purification of a variety of these guest mixtures through supramolecular strategies. SCXRD analyses showed that H1 experienced intermolecular host···host hydrogen bonding interactions between the carboxylic acid functional groups, while H2 typically demonstrated intermolecular non-classical hydrogen bonds in its complexes, forming sheets of host molecules along the c-axis. H4 preferred the “inactive” form whereas H3 assumed either an “active” or “inactive“ form. Various host···guest interactions such as π∙∙∙π, C–H∙∙∙π, C–O∙∙∙π, hydrogen bonding and other short contacts were responsible for guest retention in the crystal structures. Thermal analyses were conducted on all of the successfully formed complexes. Ton (the guest release onset temperature) and Tp (the temperature at which the guest release was most rapid) were recorded, when possible, while the mass losses associated with the guest release event were compared with those mass losses expected, in most cases. , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
The host potential of wheel-and-axle polyaromatic compounds
- Authors: Vorgers, Jarryd Allister
- Date: 2024-04
- Subjects: Supramolecular chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64426 , vital:73704
- Description: In this work, wheel-and-axle compounds 1,4-phenylene-bis(diphenylmethanol) (H1), 1,4-phenylene-bis(di-p-tolylmethanol) (H2) and 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H3) were investigated for their host behaviour in various pyridyl and heterocyclic guest mixtures. These host compounds were readily synthesized by means of Grignard addition reactions on dimethyl terephthalate, employing the aryl halides bromobenzene for H1 (73% yield), p-bromotoluene for H2 (69%) and p-bromofluorobenzene for H3 (70%). Molecular modelling calculations demonstrated that the various C-C-C angles differed between the computed low energy host conformers and those in the host molecules from their PYR-containing crystal structures. However, specified ‘torsion’ angles were in close agreement. Compound 1,4-phenylene-bis(diphenylmethanol) (H1) possessed the ability to form 1:2 host-guest (H:G) complexes with each of pyridine (PYR) and 2-, 3- and 4-methylpyridine (2MP, 3MP and 4MP). Furthermore, H1 showed preferential behaviour towards PYR and 4MP when presented with various mixtures of these four pyridines. Due to the high selectivity coefficients calculated in many instances (the selectivity coefficient, K, is a measure of the selectivity of a host compound for one particular guest in a mixture), it was demonstrated that H1 would be suitable for separations/purifications for many of the mixtures investigated in this work through host-guest chemistry strategies. (These pyridines are difficult to separate by means of the more conventional fractional distillations because of very similar boiling points.) Single crystal X-ray diffraction (SCXRD) analyses revealed that 4MP and 3MP experienced hydrogen bonds with the host molecule which were similar in distance, while the hydrogen bond distance between H1 and 4MP was shorter than that between H1 and 2MP. Furthermore, the hydrogen bond angles in complexes with the preferred PYR and 4MP guest species were more linear than in those having 2MP and 3MP. Additionally, preferred PYR and 4MP experienced significant π‧‧‧π contacts with nearby guest molecules, while disfavoured 2MP and 3MP did not interact in this fashion. Hirshfeld surface analyses demonstrated that PYR and 4MP (favoured) were involved in a greater percentage of (guest)N‧‧H(host) , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
- Authors: Vorgers, Jarryd Allister
- Date: 2024-04
- Subjects: Supramolecular chemistry
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/64426 , vital:73704
- Description: In this work, wheel-and-axle compounds 1,4-phenylene-bis(diphenylmethanol) (H1), 1,4-phenylene-bis(di-p-tolylmethanol) (H2) and 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H3) were investigated for their host behaviour in various pyridyl and heterocyclic guest mixtures. These host compounds were readily synthesized by means of Grignard addition reactions on dimethyl terephthalate, employing the aryl halides bromobenzene for H1 (73% yield), p-bromotoluene for H2 (69%) and p-bromofluorobenzene for H3 (70%). Molecular modelling calculations demonstrated that the various C-C-C angles differed between the computed low energy host conformers and those in the host molecules from their PYR-containing crystal structures. However, specified ‘torsion’ angles were in close agreement. Compound 1,4-phenylene-bis(diphenylmethanol) (H1) possessed the ability to form 1:2 host-guest (H:G) complexes with each of pyridine (PYR) and 2-, 3- and 4-methylpyridine (2MP, 3MP and 4MP). Furthermore, H1 showed preferential behaviour towards PYR and 4MP when presented with various mixtures of these four pyridines. Due to the high selectivity coefficients calculated in many instances (the selectivity coefficient, K, is a measure of the selectivity of a host compound for one particular guest in a mixture), it was demonstrated that H1 would be suitable for separations/purifications for many of the mixtures investigated in this work through host-guest chemistry strategies. (These pyridines are difficult to separate by means of the more conventional fractional distillations because of very similar boiling points.) Single crystal X-ray diffraction (SCXRD) analyses revealed that 4MP and 3MP experienced hydrogen bonds with the host molecule which were similar in distance, while the hydrogen bond distance between H1 and 4MP was shorter than that between H1 and 2MP. Furthermore, the hydrogen bond angles in complexes with the preferred PYR and 4MP guest species were more linear than in those having 2MP and 3MP. Additionally, preferred PYR and 4MP experienced significant π‧‧‧π contacts with nearby guest molecules, while disfavoured 2MP and 3MP did not interact in this fashion. Hirshfeld surface analyses demonstrated that PYR and 4MP (favoured) were involved in a greater percentage of (guest)N‧‧H(host) , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
- Full Text:
- Date Issued: 2024-04
Synthesis, characterization and host-guest complexes of supramolecular assemblies based on calixarenes and cucurbiturils
- Authors: Baa, Ebenezer
- Date: 2022-10-14
- Subjects: Supramolecular chemistry , Calixarenes , Cucurbiturils , Metal-organic frameworks , Macrocyclic compounds , Drug delivery systems
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/365621 , vital:65765 , DOI https://doi.org/10.21504/10962/365621
- Description: The field of supramolecular chemistry has grown large and wide in both deepness of understanding, range of topics covered and scope and applications. Supramolecular self-assemblies are facilitated by a wide range of non-covalent intra and inter molecular interactions that range from hydrogen bonding to π-interaction and van der Waals. Macrocyclic compounds such as cucurbiturils and calixarenes have emerged as important classes of compounds with excellent potential of forming supramolecular assemblies. The porous nature of these compounds enables them to form host-guest supramolecular complexes stabilized by diverse range of non-covalent interactions. Furthermore, these compounds contain donor atoms capable of forming bonds with metal ions to yield metal complexes with interesting porous characteristics that deviate from their traditional hydrophobic cavity. The versatile nature of the resulting pores imply that they can accommodate diverse types of guests. This work explores the synthesis and characterization of a host of calixarenes and cucurbiturils. Self-assembly of these macrocycles with various metal ions results to the formation of porous metal organic framework (MOF) complexes. Four new calixarene typed compounds obtained from aromatic aldehydes and twenty-six cucurbituril metal complexes are reported. These macrocylces and their metal complexes also form supramolecular complexes with DMSO, methanol, isoniazid hydrochloride and ciprofloxacin hydrochlorides through either self-assembly, mechanochemistry and exposure to solvent vapors. The bulk materials have been characterized using nuclear magnetic resonance spectroscopy (NMR), Fourier transformed infrared spectroscopy (FTIR), powder and single crystal diffraction techniques and thermal studies thermogravimetric analysis (TGA) and differential thermal calorimetry (DSC). Data obtained from this study reveals that calixarenes can form supramolecular complexes with a frequently used laboratory solvents with BN22 showing appreciable selectivity for DMSO sorption from a solvent mixture. These compounds also form supramolecular complexes with drug molecules such as isoniazid and ciprofloxacin. Furthermore, the data reveals that choice of synthetic route of supramolecular ensembles dictates if the guest drug molecule will occupy the intrinsic or extrinsic pores of cucurbituril complexes. Biological studies on the obtained complexes reveal that the cucurbituril complexes are non-cytotoxic while the calixarenes show antibacterial activity against Escherichia coli and Staphylococcus aureus. Additionally, the study showed that ciprofloxacin can be successfully released from a calixarene host in a simulated body fluid although the host was also found to cross the dialysis membrane. The results of this study are important in that; - they can be exploited and developed in the selective sorption of certain guests and - that they can be used in the development of drug delivery systems that play a dual role of delivery and therapeutic activity. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-10-14
- Authors: Baa, Ebenezer
- Date: 2022-10-14
- Subjects: Supramolecular chemistry , Calixarenes , Cucurbiturils , Metal-organic frameworks , Macrocyclic compounds , Drug delivery systems
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/365621 , vital:65765 , DOI https://doi.org/10.21504/10962/365621
- Description: The field of supramolecular chemistry has grown large and wide in both deepness of understanding, range of topics covered and scope and applications. Supramolecular self-assemblies are facilitated by a wide range of non-covalent intra and inter molecular interactions that range from hydrogen bonding to π-interaction and van der Waals. Macrocyclic compounds such as cucurbiturils and calixarenes have emerged as important classes of compounds with excellent potential of forming supramolecular assemblies. The porous nature of these compounds enables them to form host-guest supramolecular complexes stabilized by diverse range of non-covalent interactions. Furthermore, these compounds contain donor atoms capable of forming bonds with metal ions to yield metal complexes with interesting porous characteristics that deviate from their traditional hydrophobic cavity. The versatile nature of the resulting pores imply that they can accommodate diverse types of guests. This work explores the synthesis and characterization of a host of calixarenes and cucurbiturils. Self-assembly of these macrocycles with various metal ions results to the formation of porous metal organic framework (MOF) complexes. Four new calixarene typed compounds obtained from aromatic aldehydes and twenty-six cucurbituril metal complexes are reported. These macrocylces and their metal complexes also form supramolecular complexes with DMSO, methanol, isoniazid hydrochloride and ciprofloxacin hydrochlorides through either self-assembly, mechanochemistry and exposure to solvent vapors. The bulk materials have been characterized using nuclear magnetic resonance spectroscopy (NMR), Fourier transformed infrared spectroscopy (FTIR), powder and single crystal diffraction techniques and thermal studies thermogravimetric analysis (TGA) and differential thermal calorimetry (DSC). Data obtained from this study reveals that calixarenes can form supramolecular complexes with a frequently used laboratory solvents with BN22 showing appreciable selectivity for DMSO sorption from a solvent mixture. These compounds also form supramolecular complexes with drug molecules such as isoniazid and ciprofloxacin. Furthermore, the data reveals that choice of synthetic route of supramolecular ensembles dictates if the guest drug molecule will occupy the intrinsic or extrinsic pores of cucurbituril complexes. Biological studies on the obtained complexes reveal that the cucurbituril complexes are non-cytotoxic while the calixarenes show antibacterial activity against Escherichia coli and Staphylococcus aureus. Additionally, the study showed that ciprofloxacin can be successfully released from a calixarene host in a simulated body fluid although the host was also found to cross the dialysis membrane. The results of this study are important in that; - they can be exploited and developed in the selective sorption of certain guests and - that they can be used in the development of drug delivery systems that play a dual role of delivery and therapeutic activity. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-10-14
Synthesis, crystal structures and characterization of metal–organic framework architectures involving dinuclear copper(ii) benzoic acid derivative complexes
- Authors: Ndima, Lubabalo
- Date: 2020
- Subjects: Supramolecular chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46783 , vital:39657
- Description: Structural copper(II) complexes with aromatic carboxylic acids show a wide spectrum of coordination schemes. Studies of dicopper(II) carboxylates have been associated with a variety of interests for their catalytic, biological and magnetic applications [1]. Various novel dinuclear copper(II) complexes [Cu2(X-benzoate)4L2] with varying substituents (X = CH3, F, Cl, Br, I, NO2 & OCH3) with a desired octahedral geometry have been synthesized. The various complexes were characterized by single crystal X-ray diffraction studies, spectroscopic and thermal methods (UV/Vis, FTIR and TGA, DSC). In most cases, the structures consists of centrosymmetric dimers in which the Cu atoms show a square pyramidal CuO5 coordination. In all cases, dimeric paddle wheel complexes where two copper(II) ions are held together by four benzoates (forming syn– syn bridges between the copper atoms) and the apical coordination site occupied by a solvent ligand (L) or supramolecular linker were obtained. The dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol (solvent ligand) on one Cu(II) and the carboxylate group on an adjacent Cu(II) dimer, including interactions arising from various substituents. π–π Stacking interactions are found to be present in the various crystal structures forming 3D supramolecular array. FTIR and UV/Vis spectra of each complex have shown how the resonance and inductive effect of each substituent affects spectral data of each complex.
- Full Text:
- Date Issued: 2020
- Authors: Ndima, Lubabalo
- Date: 2020
- Subjects: Supramolecular chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/46783 , vital:39657
- Description: Structural copper(II) complexes with aromatic carboxylic acids show a wide spectrum of coordination schemes. Studies of dicopper(II) carboxylates have been associated with a variety of interests for their catalytic, biological and magnetic applications [1]. Various novel dinuclear copper(II) complexes [Cu2(X-benzoate)4L2] with varying substituents (X = CH3, F, Cl, Br, I, NO2 & OCH3) with a desired octahedral geometry have been synthesized. The various complexes were characterized by single crystal X-ray diffraction studies, spectroscopic and thermal methods (UV/Vis, FTIR and TGA, DSC). In most cases, the structures consists of centrosymmetric dimers in which the Cu atoms show a square pyramidal CuO5 coordination. In all cases, dimeric paddle wheel complexes where two copper(II) ions are held together by four benzoates (forming syn– syn bridges between the copper atoms) and the apical coordination site occupied by a solvent ligand (L) or supramolecular linker were obtained. The dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol (solvent ligand) on one Cu(II) and the carboxylate group on an adjacent Cu(II) dimer, including interactions arising from various substituents. π–π Stacking interactions are found to be present in the various crystal structures forming 3D supramolecular array. FTIR and UV/Vis spectra of each complex have shown how the resonance and inductive effect of each substituent affects spectral data of each complex.
- Full Text:
- Date Issued: 2020
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