Pub Date : 2021-06-03DOI: 10.1080/10610278.2021.1959920
Chao Shen, Rene Z. H. Phe, Isabella Fong, A. Sobolev, M. Mocerino, Massimiliano Massi, M. Ogden
ABSTRACT Driven by an interest in the impact of the para-substituent of calix[4]arenes on metal complexation and structural chemistry, studies of p-cyclohexylcalix[4]arene (L) have been carried out. The 1:1 dichloromethane and dimethylformamide solvates were found to be isostructural, and different to the typical bilayer structure often observed for p-t-butylcalix[4]arene solvates. The methanol solvate, in contrast, does form a bilayered structure but is also a 1:1 solvate, unlike the p-t-butylcalix[4]arene·2MeOH system. Lanthanoid complexation was investigated, resulting in the structural characterisation of two different DMF solvates of a 2:2 dimeric europium complex, Eu2(L–3H)2(DMF)4. A tetrazole derivative, 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-bis(tetrazole-5-ylmethoxy)calix[4]arene, has been synthesised via the intermediate 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-dicyanomethoxycalix[4]arene, with the latter compound being structurally characterised. Attempts to isolate lanthanoid clusters supported by the tetrazole derivative under conditions known to form Ln19 clusters with the p-t-butyl analogue were unsuccessful, resulting only in isolation of the ligand from the reaction mixture. Graphical abstract
{"title":"Structure, derivatisation, and metal complexation of p-cyclohexylcalix[4]arene","authors":"Chao Shen, Rene Z. H. Phe, Isabella Fong, A. Sobolev, M. Mocerino, Massimiliano Massi, M. Ogden","doi":"10.1080/10610278.2021.1959920","DOIUrl":"https://doi.org/10.1080/10610278.2021.1959920","url":null,"abstract":"ABSTRACT Driven by an interest in the impact of the para-substituent of calix[4]arenes on metal complexation and structural chemistry, studies of p-cyclohexylcalix[4]arene (L) have been carried out. The 1:1 dichloromethane and dimethylformamide solvates were found to be isostructural, and different to the typical bilayer structure often observed for p-t-butylcalix[4]arene solvates. The methanol solvate, in contrast, does form a bilayered structure but is also a 1:1 solvate, unlike the p-t-butylcalix[4]arene·2MeOH system. Lanthanoid complexation was investigated, resulting in the structural characterisation of two different DMF solvates of a 2:2 dimeric europium complex, Eu2(L–3H)2(DMF)4. A tetrazole derivative, 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-bis(tetrazole-5-ylmethoxy)calix[4]arene, has been synthesised via the intermediate 5,11,17,23-tetracyclohexyl-25,27-dihydroxy-26,28-dicyanomethoxycalix[4]arene, with the latter compound being structurally characterised. Attempts to isolate lanthanoid clusters supported by the tetrazole derivative under conditions known to form Ln19 clusters with the p-t-butyl analogue were unsuccessful, resulting only in isolation of the ligand from the reaction mixture. Graphical abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"7 1","pages":"245 - 252"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78522481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-03DOI: 10.1080/10610278.2021.1987433
Hannah R. Aziz, Wei Yao, Jacobs H. Jordan, B. Gibb
ABSTRACT The small size and high cohesiveness of water means that water-mediated interactions are strongly context dependent.As a result, there is still much to learn about how non-polar solutes and ions interact with themselves or each other.To help address this issue, we report here on a cavitand host, TMAX-Cl (2). Possessing two different binding sites, a shallow non-polar dish that binds hydrophobes, and a crown of ammoniums that bind anions, TMAX-Cl (2) provides insight into the hydrophobic and Hofmeister effects.We find that binding to the non-polar site is weak, suggesting that a larger surface area is needed for substantial binding.In contrast, binding to the crown of ammoniums is relatively strong, despite the high dielectric of water.These findings provide a better understanding of water-mediated interactions, and define the supramolecular properties of TMAX-Cl 2 as we continue our studies of this host and related water-soluble cavitands. Graphical Abstract
{"title":"Dual Binding Modes of a Small Cavitand","authors":"Hannah R. Aziz, Wei Yao, Jacobs H. Jordan, B. Gibb","doi":"10.1080/10610278.2021.1987433","DOIUrl":"https://doi.org/10.1080/10610278.2021.1987433","url":null,"abstract":"ABSTRACT The small size and high cohesiveness of water means that water-mediated interactions are strongly context dependent.As a result, there is still much to learn about how non-polar solutes and ions interact with themselves or each other.To help address this issue, we report here on a cavitand host, TMAX-Cl (2). Possessing two different binding sites, a shallow non-polar dish that binds hydrophobes, and a crown of ammoniums that bind anions, TMAX-Cl (2) provides insight into the hydrophobic and Hofmeister effects.We find that binding to the non-polar site is weak, suggesting that a larger surface area is needed for substantial binding.In contrast, binding to the crown of ammoniums is relatively strong, despite the high dielectric of water.These findings provide a better understanding of water-mediated interactions, and define the supramolecular properties of TMAX-Cl 2 as we continue our studies of this host and related water-soluble cavitands. Graphical Abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"21 1","pages":"266 - 271"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83810347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-03DOI: 10.1080/10610278.2021.1991925
Ilaria Quaratesi, Paolo Della Sala, Clotilde Capacchione, Carmen Talotta, S. Geremia, N. Hickey, Rocco Gliubizzi, Immacolata Bruno, C. Sgarlata, R. Migliore, C. Gaeta, P. Neri
ABSTRACT The two isomers 4,4´-dihydroxydiphenyl sulphone and 2,4´-dihydroxydiphenyl sulphone (bisphenol S, BPS) form inclusion complexes with β-CD in solution, in the gas phase, and in the solid state. The complexes 4,4´-BPS@β-CD and 2,4´-BPS@β-CD were studied in solution by 1D and 2D NMR experiments. Calorimetric investigation by ITC evidenced that the β-CD host shows a greater affinity for 4,4´-BPS, with a 4,4´-BPS/2,4´-BPS selectivity ratio of 6.3. In the gas phase, CID MS experiments indicate that 4,4´-BPS has a higher kinetic barrier to escape from the β-CD cavity than the isomeric 2,4´-BPS. In the solid state, the 4,4´-BPS@β-CD and 2,4´-BPS@β-CD complexes form head-to-head dimers constituted by two β-CD macrocycles, with each β-CD hosting one BPS guest. The dimers of β-CD are sealed by H-bonding interactions involving exclusively the secondary OH groups. Finally, the formation of inclusion complexes between 4,4´-BPS or 2,4´-BPS and β-CD was also followed by FT-IR, DSC, and TGA analysis. Graphical abstract
{"title":"Selective recognition of bisphenol S isomers in water by β-cyclodextrin","authors":"Ilaria Quaratesi, Paolo Della Sala, Clotilde Capacchione, Carmen Talotta, S. Geremia, N. Hickey, Rocco Gliubizzi, Immacolata Bruno, C. Sgarlata, R. Migliore, C. Gaeta, P. Neri","doi":"10.1080/10610278.2021.1991925","DOIUrl":"https://doi.org/10.1080/10610278.2021.1991925","url":null,"abstract":"ABSTRACT The two isomers 4,4´-dihydroxydiphenyl sulphone and 2,4´-dihydroxydiphenyl sulphone (bisphenol S, BPS) form inclusion complexes with β-CD in solution, in the gas phase, and in the solid state. The complexes 4,4´-BPS@β-CD and 2,4´-BPS@β-CD were studied in solution by 1D and 2D NMR experiments. Calorimetric investigation by ITC evidenced that the β-CD host shows a greater affinity for 4,4´-BPS, with a 4,4´-BPS/2,4´-BPS selectivity ratio of 6.3. In the gas phase, CID MS experiments indicate that 4,4´-BPS has a higher kinetic barrier to escape from the β-CD cavity than the isomeric 2,4´-BPS. In the solid state, the 4,4´-BPS@β-CD and 2,4´-BPS@β-CD complexes form head-to-head dimers constituted by two β-CD macrocycles, with each β-CD hosting one BPS guest. The dimers of β-CD are sealed by H-bonding interactions involving exclusively the secondary OH groups. Finally, the formation of inclusion complexes between 4,4´-BPS or 2,4´-BPS and β-CD was also followed by FT-IR, DSC, and TGA analysis. Graphical abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"2 1","pages":"295 - 308"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87372037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-03DOI: 10.1080/10610278.2021.1990291
I. Ling, Alexandre N. Sobolev
ABSTRACT Structural analysis of two multi-component complexes comprising p-sulfonatocalix[4]arene penta-anion as the host molecule and 1-methylimidazolium or 1-butylimidazolium monocation as the guest species, aquated gadolinium(III) ion along with tetraphenylphosphonium cation, is reported. An interesting process during the formation of these inclusion complexes was seen, in which a proton transfer from p-sulfonatocalix[4]arene to the neutral guest molecules took place via acid-base reaction. 1H NMR experiment confirms the formation of the host–guest complexes and the proton transfer between the calixarene and imidazolium species in solution. Careful analysis aided by CrystalExplorer, the dominant intermolecular interactions that contribute to the stabilisation of the host–guest complex formation were readily identified. Bilayer arrangement prevails in the extended structure for both complexes regardless of the type of guest species. Graphical Abstract
{"title":"Host-aided intermolecular proton transfer in the inclusion complexes of imidazole ⊂ p-sulfonatocalix[4]arene","authors":"I. Ling, Alexandre N. Sobolev","doi":"10.1080/10610278.2021.1990291","DOIUrl":"https://doi.org/10.1080/10610278.2021.1990291","url":null,"abstract":"ABSTRACT Structural analysis of two multi-component complexes comprising p-sulfonatocalix[4]arene penta-anion as the host molecule and 1-methylimidazolium or 1-butylimidazolium monocation as the guest species, aquated gadolinium(III) ion along with tetraphenylphosphonium cation, is reported. An interesting process during the formation of these inclusion complexes was seen, in which a proton transfer from p-sulfonatocalix[4]arene to the neutral guest molecules took place via acid-base reaction. 1H NMR experiment confirms the formation of the host–guest complexes and the proton transfer between the calixarene and imidazolium species in solution. Careful analysis aided by CrystalExplorer, the dominant intermolecular interactions that contribute to the stabilisation of the host–guest complex formation were readily identified. Bilayer arrangement prevails in the extended structure for both complexes regardless of the type of guest species. Graphical Abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"18 1","pages":"272 - 282"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74010433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-03DOI: 10.1080/10610278.2021.1999451
Fabiane dos Santos Carlos, C. Zanlorenzi, Fábio Souza Nunes
ABSTRACT The absorption and emission properties of three acridine-based macrocycles MAC, DAC, and TAC that contain one, two, and four fluorophore units per molecule, respectively, were interpreted and discussed based on DFT and TD-DFT calculations, molecular size, and flexibility. The molecules were tested as fluorosensors for the detection of Cd2+ ions in organic media. GRAPHICAL ABSTARCT
{"title":"A comparative study between acridine-based macrocycle chemosensor switches to Cd(II): synthesis, spectroscopy, and theoretical calculation","authors":"Fabiane dos Santos Carlos, C. Zanlorenzi, Fábio Souza Nunes","doi":"10.1080/10610278.2021.1999451","DOIUrl":"https://doi.org/10.1080/10610278.2021.1999451","url":null,"abstract":"ABSTRACT The absorption and emission properties of three acridine-based macrocycles MAC, DAC, and TAC that contain one, two, and four fluorophore units per molecule, respectively, were interpreted and discussed based on DFT and TD-DFT calculations, molecular size, and flexibility. The molecules were tested as fluorosensors for the detection of Cd2+ ions in organic media. GRAPHICAL ABSTARCT","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"38 1","pages":"318 - 324"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76978126","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-03DOI: 10.1080/10610278.2021.1981323
Y. Matsumoto, Y. Taguchi, Naruhiro Yoshida, Shugo Tokai, T. Maruyama, T. Iwasawa
ABSTRACT Four new quinoxaline-spanned cavitands having a diester hydrogen phosphate group were successfully synthesised. These phosphorous derivatives were applied in Brønsted acid-assisted catalytic conjugate addition reactions. The results were ranked with the control of diphenyl hydrogen phosphate as well as among those four cavitands. The structure–activity relationship revealed that the catalyst centre surrounded by two trans-positioned quinoxalines significantly influences reaction profile and product distribution. This comparative study provides us an intellectual basis for future catalytic cavitand chemistry and artificial enzymatic catalysis.
{"title":"Introverted Brønsted acid cavitands for selective conjugate addition reactions","authors":"Y. Matsumoto, Y. Taguchi, Naruhiro Yoshida, Shugo Tokai, T. Maruyama, T. Iwasawa","doi":"10.1080/10610278.2021.1981323","DOIUrl":"https://doi.org/10.1080/10610278.2021.1981323","url":null,"abstract":"ABSTRACT Four new quinoxaline-spanned cavitands having a diester hydrogen phosphate group were successfully synthesised. These phosphorous derivatives were applied in Brønsted acid-assisted catalytic conjugate addition reactions. The results were ranked with the control of diphenyl hydrogen phosphate as well as among those four cavitands. The structure–activity relationship revealed that the catalyst centre surrounded by two trans-positioned quinoxalines significantly influences reaction profile and product distribution. This comparative study provides us an intellectual basis for future catalytic cavitand chemistry and artificial enzymatic catalysis.","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"59 1","pages":"253 - 265"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84079833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-04DOI: 10.1080/10610278.2021.1973002
Yong Wang, Weixia Qing
ABSTRACT Currently, drug delivery systems with low toxicity and high efficacy are urgently needed to suppress cancer cells. Herein, a non-toxic and biocompatible drug carrier (mPEG-luteolin-AuNPs) was prepared, which was characteristic by SEM, FT-IR, XRD, average particle size, zeta potential and UV-Vis spectra, respectively. Considering that the morphology of supramolecular hydrogel was porous which was good for storage of drugs, a stable supramolecular hydrogel self-assembly formed based on mPEG-luteolin-AuNPs and α-cyclodextrin (α-CD) was reported. Then, supramolecular hydrogel loaded doxorubicin hydrochloride (DOX) and sustained DOX release. Meanwhile, in vitro experiments clearly demonstrated that DOX of hydrogel (mPEG-luteolin-AuNPs/DOX) was biologically active, similar to free DOX, but with better cytotoxicity to human glioblastoma cells (U-87 MG) because of its controllable release. Our findings indicated that mPEG-luteolin-AuNPs/DOX might be promising delivery systems for anticancer chemotherapy. GRAPHICAL ABSTRACT
{"title":"The construction of gold hybrid supramolecular hydrogels for doxorubicin delivery","authors":"Yong Wang, Weixia Qing","doi":"10.1080/10610278.2021.1973002","DOIUrl":"https://doi.org/10.1080/10610278.2021.1973002","url":null,"abstract":"ABSTRACT Currently, drug delivery systems with low toxicity and high efficacy are urgently needed to suppress cancer cells. Herein, a non-toxic and biocompatible drug carrier (mPEG-luteolin-AuNPs) was prepared, which was characteristic by SEM, FT-IR, XRD, average particle size, zeta potential and UV-Vis spectra, respectively. Considering that the morphology of supramolecular hydrogel was porous which was good for storage of drugs, a stable supramolecular hydrogel self-assembly formed based on mPEG-luteolin-AuNPs and α-cyclodextrin (α-CD) was reported. Then, supramolecular hydrogel loaded doxorubicin hydrochloride (DOX) and sustained DOX release. Meanwhile, in vitro experiments clearly demonstrated that DOX of hydrogel (mPEG-luteolin-AuNPs/DOX) was biologically active, similar to free DOX, but with better cytotoxicity to human glioblastoma cells (U-87 MG) because of its controllable release. Our findings indicated that mPEG-luteolin-AuNPs/DOX might be promising delivery systems for anticancer chemotherapy. GRAPHICAL ABSTRACT","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"6 1","pages":"202 - 210"},"PeriodicalIF":3.3,"publicationDate":"2021-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87314088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-04DOI: 10.1080/10610278.2021.1959036
Qing Chang, Tao Ma, W. Ding, Lin Zhang, Xiaohong Cheng
ABSTRACT Bolaamphiphilies with D-A-D type π-conjugated rigid cores composed by thiophenes as donors (D) and benzothiadiazole (BTD) as central acceptor (A) have been synthesised. Their self-assemblies and photophysical properties were investigated by polarising optical microscope, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Such compounds can self-assemble into honeycomb cylinder mesophases with Colhex∆/p6mm and Colsqu/p4mm lattices in their pure states as well as organogels with different morphologies in organic solvents. Their absorption spectra cover nearly the entire visible light range and their band gaps are relatively low. Tetrathiophene BTD based bolaamphilphiles (BT4/n ) with higher D/A ratios than the bisthiophene BTD bolaamphilphiles (BT2/n ) can self-assemble into more ordered nanostructures in both bulk states and solution. Both the absorption and emission peaks of BT4/n are strongly red shifted. The influence of the molecular conformation, the conjugated core length, as well as the D/A ratio on the self-assemble and photophysical characteristics of such D-A-D bolaamphiphiles are discussed. GRAPHICAL ABSTRACT
{"title":"Thiophene-benzothiadiazole based donor–acceptor–donor (D-A-D) bolaamphiphiles, self-assembly and photophysical properties","authors":"Qing Chang, Tao Ma, W. Ding, Lin Zhang, Xiaohong Cheng","doi":"10.1080/10610278.2021.1959036","DOIUrl":"https://doi.org/10.1080/10610278.2021.1959036","url":null,"abstract":"ABSTRACT Bolaamphiphilies with D-A-D type π-conjugated rigid cores composed by thiophenes as donors (D) and benzothiadiazole (BTD) as central acceptor (A) have been synthesised. Their self-assemblies and photophysical properties were investigated by polarising optical microscope, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Such compounds can self-assemble into honeycomb cylinder mesophases with Colhex∆/p6mm and Colsqu/p4mm lattices in their pure states as well as organogels with different morphologies in organic solvents. Their absorption spectra cover nearly the entire visible light range and their band gaps are relatively low. Tetrathiophene BTD based bolaamphilphiles (BT4/n ) with higher D/A ratios than the bisthiophene BTD bolaamphilphiles (BT2/n ) can self-assemble into more ordered nanostructures in both bulk states and solution. Both the absorption and emission peaks of BT4/n are strongly red shifted. The influence of the molecular conformation, the conjugated core length, as well as the D/A ratio on the self-assemble and photophysical characteristics of such D-A-D bolaamphiphiles are discussed. GRAPHICAL ABSTRACT","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"32 1","pages":"174 - 182"},"PeriodicalIF":3.3,"publicationDate":"2021-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81164308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-04DOI: 10.1080/10610278.2021.1955120
Alex T. O’Neil, Ningjin Zhang, J. A. Harrison, S. Goldup, Jonathan A. Kitchen
ABSTRACT The well-known lanthanide-binding motif, 2,6-pyridinedicarboxamide, has been functionalised with peripheral substituents using copper-catalysed azide alkyne coupling (CuAAC) to develop new symmetrical ‘clicked’ N2,N6-bis((1-(X)-1H-1,2,3,-triazol-4-yl)methyl)pyridine- 2,6-dicarboxamide (where X = ethyl (1) benzyl (2) and 2-naphthyl (3)). These ligands have been successfully coordinated with trivalent lanthanide ions (europium, terbium, and lanthanum) forming [Ln(L)3](CF3SO3)3 complexes. The ligands act as effective antennae for Eu3+ and Tb3+ complexes, which exhibit the characteristic sensitised emission profiles. The ability of 1–3 to assemble into 1:3 M:L systems in solution was investigated using UV-Vis, fluorescence, and NMR. Finally, density functional calculations of the ground state La3+ complexes have been carried out and show similar geometry and coordination parameters to those with available crystallographic data. The facile and modular synthesis of these ‘clicked’ PDC-based ligands makes these compounds excellent candidates for luminescent supramolecular materials development.
{"title":"Synthesis, photophysical and assembly studies of novel luminescent lanthanide(III) complexes of 1,2,3-triazolyl-pyridine-2,6-dicarboxamide-based ligands","authors":"Alex T. O’Neil, Ningjin Zhang, J. A. Harrison, S. Goldup, Jonathan A. Kitchen","doi":"10.1080/10610278.2021.1955120","DOIUrl":"https://doi.org/10.1080/10610278.2021.1955120","url":null,"abstract":"ABSTRACT The well-known lanthanide-binding motif, 2,6-pyridinedicarboxamide, has been functionalised with peripheral substituents using copper-catalysed azide alkyne coupling (CuAAC) to develop new symmetrical ‘clicked’ N2,N6-bis((1-(X)-1H-1,2,3,-triazol-4-yl)methyl)pyridine- 2,6-dicarboxamide (where X = ethyl (1) benzyl (2) and 2-naphthyl (3)). These ligands have been successfully coordinated with trivalent lanthanide ions (europium, terbium, and lanthanum) forming [Ln(L)3](CF3SO3)3 complexes. The ligands act as effective antennae for Eu3+ and Tb3+ complexes, which exhibit the characteristic sensitised emission profiles. The ability of 1–3 to assemble into 1:3 M:L systems in solution was investigated using UV-Vis, fluorescence, and NMR. Finally, density functional calculations of the ground state La3+ complexes have been carried out and show similar geometry and coordination parameters to those with available crystallographic data. The facile and modular synthesis of these ‘clicked’ PDC-based ligands makes these compounds excellent candidates for luminescent supramolecular materials development.","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"24 1","pages":"160 - 173"},"PeriodicalIF":3.3,"publicationDate":"2021-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81038416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-04DOI: 10.1080/10610278.2021.1975710
Ergin Yalçın
ABSTRACT A facile and versatile procedure for the synthesis of novel functionalised 10-(1H-indol-3-yl)acenaphtho[1,2-d]pyrimidin-8-amine (compound 4) has been described. The novel intermediate enone (3) and pyrimidine derivatives (4) were characterised by using FT-IR, NMR and MS. Moreover, the photophysical properties of compound 4 and its interaction with HSA (Human Serum Albumin) have been investigated by means of photometric and fluorimetric titration. Compound 4 showed the increase in fluorescence and hypsochromic shift of its maximum upon the addition of HSA that interaction is supported by molecular docking. Overall, Compound 4 has promising affinity towards HSA which was not previously reported for any fused acenaphtenone–pyrimidine hybrid analogues. Graphical abstract
{"title":"Synthesis of novel fused acenaphtopyrimidine hybrid, its photophysical properties and HSA interaction","authors":"Ergin Yalçın","doi":"10.1080/10610278.2021.1975710","DOIUrl":"https://doi.org/10.1080/10610278.2021.1975710","url":null,"abstract":"ABSTRACT A facile and versatile procedure for the synthesis of novel functionalised 10-(1H-indol-3-yl)acenaphtho[1,2-d]pyrimidin-8-amine (compound 4) has been described. The novel intermediate enone (3) and pyrimidine derivatives (4) were characterised by using FT-IR, NMR and MS. Moreover, the photophysical properties of compound 4 and its interaction with HSA (Human Serum Albumin) have been investigated by means of photometric and fluorimetric titration. Compound 4 showed the increase in fluorescence and hypsochromic shift of its maximum upon the addition of HSA that interaction is supported by molecular docking. Overall, Compound 4 has promising affinity towards HSA which was not previously reported for any fused acenaphtenone–pyrimidine hybrid analogues. Graphical abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"45 1","pages":"222 - 230"},"PeriodicalIF":3.3,"publicationDate":"2021-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79946944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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