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Design and Synthesis of Macrocyclic Compounds
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Design and Synthesis of Macrocyclic Compounds

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 32472

Special Issue Editor

Dr. Vladimir Burilov

E-Mail Website
Guest Editor
Department of Organic Chemistry, Kazan Federal University, 420008 Kazan, Russia
Interests: calixarenes; click chemistry; NHC complexes; green chemistry; functional amphiphiles

Special Issue Information

Dear Colleagues,

The chemistry of macrocyclic compounds has a long history. From simple annulenes to powerful antibiotics, these molecules are united by one thing—the presence of a molecular cavity. Due to this property, macrocyclic molecules are unique synthons in supramolecular chemistry capable of intermolecular guest–host interactions with other molecules. Supramolecular chemistry, which originated in the early 1970s, continues its triumphant march on the frontier of sciences, combining chemistry, biology, physics, medicine, materials science, etc. Recently, of particular interest are the functional supramolecular macrocyclic systems capable of self-organization, which makes it possible to obtain smart materials on their basis for sensing, targeted drug delivery, and catalysis in green media. Changes in the structure and the introduction of new motifs into the macrocyclic framework allow researchers to modify existing ones and discover new properties of these molecules.

This Special Issue aims to familiarize readers with the most modern trends and achievements in the field of macrocyclic chemistry with a special focus on both the synthetic chemistry of macrocyclic compounds as well as the usage of macrocyclic compounds in molecular recognition, nanotechnology, catalysis, and biotechnology. 

Dr. Vladimir Burilov
Guest Editor

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • macrocycles
  • molecular recognition
  • catalysis
  • supramolecular chemistry
  • medical macrocyclic chemistry
  • macrocyclic amphiphiles

Published Papers (17 papers)

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Research

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12 pages, 1750 KiB  
Communication
Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure
by Pavel Yudaev, Anastasia Konstantinova, Vladimir Volkov and Evgeniy Chistyakov
Molecules 2023, 28(18), 6571; https://doi.org/10.3390/molecules28186571 - 11 Sep 2023
Cited by 1 | Viewed by 1106
Abstract
Condensation of hexakis-2-(formylphenoxy)cyclotriphosphazene with malonic acid yielded hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene (2-CEPP), whose structure was confirmed by 31P, 1H, 13C NMR spectroscopy and MALDI-TOF mass spectrometry. A quantum-chemical calculation for the 2-CEPP molecule using the ab initio methods in the 6-311G** basis [...] Read more.
Condensation of hexakis-2-(formylphenoxy)cyclotriphosphazene with malonic acid yielded hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene (2-CEPP), whose structure was confirmed by 31P, 1H, 13C NMR spectroscopy and MALDI-TOF mass spectrometry. A quantum-chemical calculation for the 2-CEPP molecule using the ab initio methods in the 6-311G** basis set and the DFT-PBE0/6-311g** method was performed with geometry optimization of all parameters by the standard gradient method. The acid strength of 2-CEPP was theoretically estimated. Using the small-angle X-ray scattering method, it was found that 2-CEPP is an amorphous substance, which, when heated, can transform into a crystalline state. However, when heated at 370 °C, 2-CEPP undergoes decarboxylation and polymerization to form an insoluble heat-resistant product. The occurrence of decarboxylation and polymerization reactions in the formed styrene fragments was confirmed by thermal (differential-scanning calorimetry) and spectral (solid-state 13C NMR spectroscopy) analysis. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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12 pages, 3177 KiB  
Article
Recognition Site Modifiable Macrocycle: Synthesis, Functional Group Variation and Structural Inspection
by Linmeng Fan, Min Du, Lichun Kong, Yan Cai and Xiaobo Hu
Molecules 2023, 28(3), 1338; https://doi.org/10.3390/molecules28031338 - 31 Jan 2023
Viewed by 1333
Abstract
Traditional macrocyclic molecules encode recognition sites in their structural backbones, which limits the variation of the recognition sites and thus, would restrict the adjustment of recognition properties. Here, we report a new oligoamide-based macrocycle capable of varying the recognition functional groups by post-synthesis [...] Read more.
Traditional macrocyclic molecules encode recognition sites in their structural backbones, which limits the variation of the recognition sites and thus, would restrict the adjustment of recognition properties. Here, we report a new oligoamide-based macrocycle capable of varying the recognition functional groups by post-synthesis modification on its structural backbone. Through six steps of common reactions, the parent macrocycle (9) can be produced in gram scale with an overall yield of 31%. The post-synthesis modification of 9 to vary the recognition sites are demonstrated by producing four different macrocycles (10–13) with distinct functional groups, 2-methoxyethoxyl (10), hydroxyl (11), carboxyl (12) and amide (13), respectively. The 1H NMR study suggests that the structure of these macrocycles is consistent with our design, i.e., forming hydrogen bonding network at both rims of the macrocyclic backbone. The 1H-1H NOESY NMR study indicates the recognition functional groups are located inside the cavity of macrocycles. At last, a preliminary molecular recognition study shows 10 can recognize n-octyl-β-D-glucopyranoside (14) in chloroform. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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23 pages, 5466 KiB  
Article
Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence—Synthesis, Structure, and Catalytic Activity
by Alexey N. Bilyachenko, Ivan S. Arteev, Victor N. Khrustalev, Anna Y. Zueva, Lidia S. Shul’pina, Elena S. Shubina, Nikolay S. Ikonnikov and Georgiy B. Shul’pin
Molecules 2023, 28(3), 1211; https://doi.org/10.3390/molecules28031211 - 26 Jan 2023
Cited by 6 | Viewed by 1775
Abstract
A family of unusual octacopper cage methylsilsesquioxanes 1–4 were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages 1–4 due to variation of (i) additional alkaline metal [...] Read more.
A family of unusual octacopper cage methylsilsesquioxanes 1–4 were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages 1–4 due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of Cu8K2-based compound 2) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of Cu8Cs2-based compound 4). Cu8Cs2-complex 4 was evaluated in the catalysis of alkanes and alcohols. Complex 4 exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex 4 as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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11 pages, 2675 KiB  
Article
Comparison of Photophysical Properties of Lanthanide(III) Complexes of DTTA- or DO3A-Appended Aryl-2,2′-Bipyridines
by Alexey P. Krinochkin, Maria I. Valieva, Ekaterina S. Starnovskaya, Yaroslav K. Shtaitz, Dmitry S. Kopchuk, Olga S. Taniya, Grigory A. Kim, Vadim A. Shevyrin, Grigory V. Zyryanov and Oleg N. Chupakhin
Molecules 2023, 28(2), 724; https://doi.org/10.3390/molecules28020724 - 11 Jan 2023
Viewed by 1378
Abstract
New Tb(III) and Eu(III) complexes based on aryl-2,2′-bipyridine ligands with a cyclic DO3A chelating unit appended in the alpha position of the bipyridine core were synthesized. The photophysical properties of these complexes were compared with those of complexes of ligands with identical aryl-2,2′-bipyridine [...] Read more.
New Tb(III) and Eu(III) complexes based on aryl-2,2′-bipyridine ligands with a cyclic DO3A chelating unit appended in the alpha position of the bipyridine core were synthesized. The photophysical properties of these complexes were compared with those of complexes of ligands with identical aryl-2,2′-bipyridine chromophores, but with an acyclic DTTA residue as an additional chelating site in the alpha position of the bipyridine core. The nature of the polyaminocarboxylic acid fragments was found to have a significant influence on the luminescence. For some of the Eu(III) complexes, upon the transition from acyclic DTTA- to the cyclic DO3A-appended ligands, a noticeable increase in the intensity of Eu(III) luminescence was observed, with an increase in the quantum yield of up to 2.55 times. In contrast, for most of the Tb(III) complexes, a similar transition resulted in a noticeable decrease in the luminescence intensity of the Tb(III) cation. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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21 pages, 5618 KiB  
Article
Polyoxa- and Polyazamacrocycles Incorporating 6,7-Diaminoquinoxaline Moiety: Synthesis and Application as Tunable Optical pH-Indicators in Aqueous Solution
by Igor A. Kurashov, Alisa D. Kharlamova, Anton S. Abel, Alexei D. Averin and Irina P. Beletskaya
Molecules 2023, 28(2), 512; https://doi.org/10.3390/molecules28020512 - 04 Jan 2023
Cited by 1 | Viewed by 1356
Abstract
Synthetic approach to fluorescent polyaza- and polyoxadiazamacrocycles comprising a structural fragment of 6,7-diamino-2,3-diphenylquinoxaline has been elaborated using Pd-catalyzed amination providing target compounds in yields up to 77%. A series of nine novel N- and N,O-containing macrocyclic ligands differing by [...] Read more.
Synthetic approach to fluorescent polyaza- and polyoxadiazamacrocycles comprising a structural fragment of 6,7-diamino-2,3-diphenylquinoxaline has been elaborated using Pd-catalyzed amination providing target compounds in yields up to 77%. A series of nine novel N- and N,O-containing macrocyclic ligands differing by the number of donor sites and cavity size has been obtained. These compounds possess well-pronounced fluorescent properties with emission maxima in a blue region in aprotic solvents and high quantum yields of fluorescence, while in proton media, fluorescence shifts towards the green region of the spectrum. Using macrocycles 5c and 5e as examples, we have shown that such compounds can serve as dual-channel (colorimetric and fluorimetric) pH indicators in water media, with pH transition point and response being dependent on the macrocycle structure due to different sequences of protonation steps. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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12 pages, 2099 KiB  
Article
Synthesis, Structure, and Spectral-Luminescent Properties of Peripherally Fluorinated Mg(II) and Zn(II) Octaphenyltetraazaporphyrins
by Alexey Rusanov, Natalya Chizhova and Nugzar Mamardashvili
Molecules 2022, 27(23), 8619; https://doi.org/10.3390/molecules27238619 - 06 Dec 2022
Cited by 3 | Viewed by 1166
Abstract
The cyclization of di-(2,6-difluorophenyl)maleindinitrile with magnesium(II) and zinc(II) acetates in boiling ethylene glycol is applied to synthesize Mg(II) and Zn(II) complexes of the octa-(2,6-difluorophenyl)tetraazaporphyrin. The compounds are identified by UV–Vis, 1H NMR, and mass spectrometry methods. A comparative analysis is performed of [...] Read more.
The cyclization of di-(2,6-difluorophenyl)maleindinitrile with magnesium(II) and zinc(II) acetates in boiling ethylene glycol is applied to synthesize Mg(II) and Zn(II) complexes of the octa-(2,6-difluorophenyl)tetraazaporphyrin. The compounds are identified by UV–Vis, 1H NMR, and mass spectrometry methods. A comparative analysis is performed of the spectral-luminescent properties of magnesium and zinc octaaryltetraazaporphyrinates and their dependence on the number and position of the fluorine atoms in the macrocycle phenyl fragments. The DFT method is used to optimize the geometry of the synthesized complexes. Machine learning methods and QSPR are applied to predict the Soret band wavelength in the UV–V is spectra of the complexes described. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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16 pages, 5194 KiB  
Article
Cycloalkyl Groups as Building Blocks of Artificial Carbohydrate Receptors: Studies with Macrocycles Bearing Flexible Side-Arms
by Betty Leibiger, Manuel Stapf and Monika Mazik
Molecules 2022, 27(21), 7630; https://doi.org/10.3390/molecules27217630 - 07 Nov 2022
Cited by 6 | Viewed by 1429
Abstract
The cyclopentyl group was expected to act as a building block for artificial carbohydrate receptors and to participate in van der Waals contacts with the carbohydrate substrate in a similar way as observed for the pyrrolidine ring of proline in the crystal structures [...] Read more.
The cyclopentyl group was expected to act as a building block for artificial carbohydrate receptors and to participate in van der Waals contacts with the carbohydrate substrate in a similar way as observed for the pyrrolidine ring of proline in the crystal structures of protein-carbohydrate complexes. Systematic binding studies with a series of 1,3,5-trisubstituted 2,4,6-triethylbenzenes bearing various cycloalkyl groups as recognition units provided indications of the involvement of these groups in the complexation process and showed the influence of the ring size on the receptor efficiency. Representatives of compounds that exhibit a macrocyclic backbone and flexible side arms were now chosen as further model systems to investigate whether the previously observed effects represent a general trend. Binding studies with these macrocycles towards β-D-glucopyranoside, an all-equatorial substituted carbohydrate substrate, included 1H NMR spectroscopic titrations and microcalorimetric investigations. The performed studies confirmed the previously observed tendency and showed that the compound bearing cyclohexyl groups displays the best binding properties. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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19 pages, 11006 KiB  
Article
Experimental and Theoretical Studies of the Optical Properties of the Schiff Bases and Their Materials Obtained from o-Phenylenediamine
by Magdalena Barwiolek, Dominika Jankowska, Anna Kaczmarek-Kędziera, Slawomir Wojtulewski, Lukasz Skowroński, Tomasz Rerek, Paweł Popielarski and Tadeusz M. Muziol
Molecules 2022, 27(21), 7396; https://doi.org/10.3390/molecules27217396 - 31 Oct 2022
Cited by 1 | Viewed by 1562
Abstract
Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and [...] Read more.
Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of L1 and L2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk tert-butyl groups in L2. The luminescence of L1 and L2 in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of L1 was observed (λex = 350 nm). For L2, this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λex = 350 nm) for L1 and L2, respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for L1/Si and L2/Si samples, respectively. Furthermore, the materials of the L1/Si and L2/Si exhibited broad emission. This feature can allow for using these compounds in LED diodes. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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16 pages, 4139 KiB  
Article
Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb3-Luminescence via Upper-Rim Substitution+
by Sergey N. Podyachev, Svetlana N. Sudakova, Rustem R. Zairov, Victor V. Syakaev, Alexey N. Masliy, Michal Dusek, Aidar T. Gubaidullin, Alexey P. Dovzhenko, Daina N. Buzyurova, Dmitry V. Lapaev, Gulnaz Sh. Mambetova, Vasily M. Babaev, Andrey M. Kuznetsov and Asiya R. Mustafina
Molecules 2022, 27(20), 6793; https://doi.org/10.3390/molecules27206793 - 11 Oct 2022
Cited by 2 | Viewed by 1085
Abstract
The present work introduces the series of thiacalix[4]arenes (H4L) bearing different upper-rim substituents (R = H, Br, NO2) for rational design of ligands providing an antenna-effect on the NIR Yb3+-centered luminescence of their Yb3+ complexes. The [...] Read more.
The present work introduces the series of thiacalix[4]arenes (H4L) bearing different upper-rim substituents (R = H, Br, NO2) for rational design of ligands providing an antenna-effect on the NIR Yb3+-centered luminescence of their Yb3+ complexes. The unusual inclusive self-assembly of H3L− (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb3+:2HL3−] leads to efficient sensitizing of the Yb3+ luminescence for H4L (Br, NO2), while poor sensitizing is observed for ligand H4L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl3 and H4L(NO2) has revealed the transformation of the dimeric complexes into [4Yb3+:2L4−] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H4L(R = NO2), where the triplet level at 567 nm (17,637 cm−1) arisen from ILCT provides efficient sensitizing of the Yb3+ luminescence. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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18 pages, 4866 KiB  
Article
Multicomponent Molecular Systems Based on Porphyrins, 1,3,5-Triazine and Carboranes: Synthesis and Characterization
by Victoria M. Alpatova, Evgeny G. Rys, Elena G. Kononova, Ekaterina A. Khakina, Alina A. Markova, Anna V. Shibaeva, Vladimir A. Kuzmin and Valentina A. Ol’shevskaya
Molecules 2022, 27(19), 6200; https://doi.org/10.3390/molecules27196200 - 21 Sep 2022
Cited by 1 | Viewed by 1525
Abstract
2,4,6-Trichloro-1,3,5-triazine (cyanuric chloride) is an excellent coupling reagent for the preparation of highly structured multifunctional molecules. Three component systems based on porphyrin, cyanuric chloride and carborane clusters were prepared by a one-pot stepwise amination of cyanuric chloride with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, followed by replacement of [...] Read more.
2,4,6-Trichloro-1,3,5-triazine (cyanuric chloride) is an excellent coupling reagent for the preparation of highly structured multifunctional molecules. Three component systems based on porphyrin, cyanuric chloride and carborane clusters were prepared by a one-pot stepwise amination of cyanuric chloride with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, followed by replacement of the remaining chlorine atoms with carborane S- or N-nucleophiles. Some variants of 1,3,5-triazine derivatives containing porphyrin, carborane and residues of biologically active compounds such as maleimide, glycine methyl ester as well as thioglycolic acid, mercaptoethanol and hexafluoroisopropanol were also prepared. A careful control of the reaction temperature during the substitution reactions will allow the synthesis of desired compounds in a good to high yields. The structures of synthesized compounds were determined with UV-vis, IR, 1H NMR, 11B NMR, MALDI-TOF or LC-MS spectroscopic data. The dark and photocytotoxicity as well as intracellular localization and photoinduced cell death for compounds 8, 9, 17, 18 and 24 were evaluated. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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17 pages, 3636 KiB  
Article
Novel Hybrid Benzoazacrown Ligand as a Chelator for Copper and Lead Cations: What Difference Does Pyridine Make
by Bayirta V. Egorova, Lyubov S. Zamurueva, Anastasia D. Zubenko, Anna V. Pashanova, Artem A. Mitrofanov, Anna B. Priselkova, Yuri V. Fedorov, Alexander L. Trigub, Olga A. Fedorova and Stepan N. Kalmykov
Molecules 2022, 27(10), 3115; https://doi.org/10.3390/molecules27103115 - 12 May 2022
Cited by 2 | Viewed by 1854
Abstract
A synthetic procedure for the synthesis of azacrown ethers with a combination of pendant arms has been developed and the synthesized ligand, characterized by various techniques, was studied. The prepared benzoazacrown ether with hybrid pendant arms and its complexes with copper and lead [...] Read more.
A synthetic procedure for the synthesis of azacrown ethers with a combination of pendant arms has been developed and the synthesized ligand, characterized by various techniques, was studied. The prepared benzoazacrown ether with hybrid pendant arms and its complexes with copper and lead cations were studied in terms of biomedical applications. Similarly to a fully acetate analog, the new one binds both cations with close stability constants, despite the decrease in both constants. The calculated geometry of the complexes correlate with the data from X-ray absorption and NMR spectroscopy. Coordination of both cations differs due to the difference between the ionic radii. However, these chelation modes provide effective shielding of cations in both cases, that was shown by the stability of their complexes in the biologically relevant media towards transchelation and transmetallation. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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12 pages, 4537 KiB  
Article
New Calix[4]arene—Fluoresceine Conjugate by Click Approach—Synthesis and Preparation of Photocatalytically Active Solid Lipid Nanoparticles
by Vladimir A. Burilov, Alina A. Artemenko, Ramilya I. Garipova, Rezeda R. Amirova, Aigul M. Fatykhova, Julia A. Borisova, Diana A. Mironova, Elza D. Sultanova, Vladimir G. Evtugyn, Svetlana E. Solovieva and Igor S. Antipin
Molecules 2022, 27(8), 2436; https://doi.org/10.3390/molecules27082436 - 09 Apr 2022
Cited by 7 | Viewed by 2283
Abstract
New fluorescent systems for photocatalysis, sensors, labeling, etc., are in great demand. Amphiphilic ones are of special interest since they can form functional colloidal systems that can be used in aqueous solutions. A new macrocycle platform for click chemistry and its adduct with [...] Read more.
New fluorescent systems for photocatalysis, sensors, labeling, etc., are in great demand. Amphiphilic ones are of special interest since they can form functional colloidal systems that can be used in aqueous solutions. A new macrocycle platform for click chemistry and its adduct with o-propargylfluoresceine was synthesized and characterized using modern physical techniques. Nanosized solid lipid nanoparticles (SLNs) from the calixarene—fluoresceine adduct were synthesized through the solvent injection technique and well-characterized in the solution and in solid state using light-scattering and microscopy methods. The maximum fluorescence intensity of the SLNs was found to be in the pH range from 7 to 10. The Förster resonance energy transfer (FRET) efficiency from SLNs to rhodamine 6g was found to be 97.8%. Finally, pure SLNs and the FRET system SLNs—Rh6G were tested in model photocatalytic ipso oxidative hydroxylation of phenylboronic acid under blue LED light. The SLNs—Rh6G system was found to be the best, giving an almost qualitative phenol yield, which was shown by HPLC-UV analysis. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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12 pages, 2970 KiB  
Article
Structure–Activity Relationship of the Thiacalix[4]arenes Family with Sulfobetaine Fragments: Self-Assembly and Cytotoxic Effect against Cancer Cell Lines
by Luidmila Yakimova, Aisylu Kunafina, Aigul Nugmanova, Pavel Padnya, Alexandra Voloshina, Konstantin Petrov and Ivan Stoikov
Molecules 2022, 27(4), 1364; https://doi.org/10.3390/molecules27041364 - 17 Feb 2022
Cited by 4 | Viewed by 1905
Abstract
Regulating the structure of macrocyclic host molecules and supramolecular assemblies is crucial because the structure–activity relationship often plays a role in governing the properties of these systems. Herein, we propose and develop an approach to the synthesis of the family of sulfobetaine functionalized [...] Read more.
Regulating the structure of macrocyclic host molecules and supramolecular assemblies is crucial because the structure–activity relationship often plays a role in governing the properties of these systems. Herein, we propose and develop an approach to the synthesis of the family of sulfobetaine functionalized thiacalix[4]arenes with regulation of the self-assembly and cytotoxic effect against cancer cell lines. The dynamic light scattering method showed that the synthesized macrocycles in cone, partial cone and 1,3-alternate conformations form submicron-sized particles with Ag+ in water, but the particle size and polydispersity of the systems studied depend on the macrocycle conformation. Based on the results obtained by 1H and 1H-1H NOESY NMR spectroscopy and transmission electron microscopy for the macrocycles and their aggregates with Ag+, a coordination scheme for the Ag+ and different conformations of p-tert-butylthiacalix[4]arene functionalized with sulfobetaine fragments was proposed. The type of coordination determines the different shapes of the associates. Cytotoxic properties are shown to be controlled by the shape of associates, with the highest activity demonstrated by thiacalix[4]arenes in partial cone conformation. This complex partial cone/Ag+ is two times higher than the reference drug imatinib mesylate. High selectivity against cervical carcinoma cell line indicates the prospect of their using as components of new anticancer system. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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17 pages, 3280 KiB  
Article
Low-Symmetry Phthalocyanines Bearing Carboxy-Groups: Synthesis, Spectroscopic and Quantum-Chemical Characterization
by Dmitry A. Bunin, Nobuhle Ndebele, Alexander G. Martynov, John Mack, Yulia G. Gorbunova and Tebello Nyokong
Molecules 2022, 27(2), 524; https://doi.org/10.3390/molecules27020524 - 14 Jan 2022
Cited by 2 | Viewed by 1973
Abstract
The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the [...] Read more.
The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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Review

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36 pages, 7320 KiB  
Review
Modern Developments in Bifunctional Chelator Design for Gallium Radiopharmaceuticals
by Patrick R. W. J. Davey and Brett M. Paterson
Molecules 2023, 28(1), 203; https://doi.org/10.3390/molecules28010203 - 26 Dec 2022
Cited by 8 | Viewed by 3770
Abstract
The positron-emitting radionuclide gallium-68 has become increasingly utilised in both preclinical and clinical settings with positron emission tomography (PET). The synthesis of radiochemically pure gallium-68 radiopharmaceuticals relies on careful consideration of the coordination chemistry. The short half-life of 68 min necessitates rapid quantitative [...] Read more.
The positron-emitting radionuclide gallium-68 has become increasingly utilised in both preclinical and clinical settings with positron emission tomography (PET). The synthesis of radiochemically pure gallium-68 radiopharmaceuticals relies on careful consideration of the coordination chemistry. The short half-life of 68 min necessitates rapid quantitative radiolabelling (≤10 min). Desirable radiolabelling conditions include near-neutral pH, ambient temperatures, and low chelator concentrations to achieve the desired apparent molar activity. This review presents a broad overview of the requirements of an efficient bifunctional chelator in relation to the aqueous coordination chemistry of gallium. Developments in bifunctional chelator design and application are then presented and grouped according to eight categories of bifunctional chelator: the macrocyclic chelators DOTA and TACN; the acyclic HBED, pyridinecarboxylates, siderophores, tris(hydroxypyridinones), and DTPA; and the mesocyclic diazepines. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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28 pages, 13783 KiB  
Review
Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes
by Jerzy Lisowski
Molecules 2022, 27(13), 4097; https://doi.org/10.3390/molecules27134097 - 25 Jun 2022
Cited by 12 | Viewed by 2880
Abstract
The condensation of aromatic dialdehydes with chiral diamines, such as 1,2-trans-diaminocyclohexane, leads to various enantiopure or meso-type macrocyclic Schiff bases, including [2 + 2], [3 + 3], [4 + 4], [6 + 6] and [8 + 8] condensation products. Unlike [...] Read more.
The condensation of aromatic dialdehydes with chiral diamines, such as 1,2-trans-diaminocyclohexane, leads to various enantiopure or meso-type macrocyclic Schiff bases, including [2 + 2], [3 + 3], [4 + 4], [6 + 6] and [8 + 8] condensation products. Unlike most cases of macrocycle synthesis, the [3 + 3] macrocycles of this type are sometimes obtained in high yields by direct condensation without a metal template. Macrocycles of other sizes from this family can often be selectively obtained in high yields by a suitable choice of metal template, solvent, or chirality of the building blocks. In particular, the application of a cadmium(II) template results in the expansion of the [2 + 2] macrocycles into giant [6 + 6] and [8 + 8] macrocycles. These imine macrocycles can be reduced to the corresponding macrocyclic amines which can act as hosts for the binding of multiple cations or multiple anions. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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26 pages, 7248 KiB  
Review
Insights on the Synthesis of N-Heterocycles Containing Macrocycles and Their Complexion and Biological Properties
by Fouad Malek, Tarik Harit, Mounir Cherfi and Bonglee Kim
Molecules 2022, 27(7), 2123; https://doi.org/10.3390/molecules27072123 - 25 Mar 2022
Cited by 10 | Viewed by 2463
Abstract
Macrocyclic chemistry has been extensively developed over the past several decades. In fact, the architecture of new macrocyclic models has undergone exponential growth to offer molecules with specific properties. In this context, an attempt is made in this study to provide an overview [...] Read more.
Macrocyclic chemistry has been extensively developed over the past several decades. In fact, the architecture of new macrocyclic models has undergone exponential growth to offer molecules with specific properties. In this context, an attempt is made in this study to provide an overview of some synthetic methods allowing the elaboration of N-heterocycles containing macrocycles (imidazole, triazole, tetrazole, and pyrazole), as well as their applications in the complexation of metal cations or as pharmacological agents. Full article
(This article belongs to the Special Issue Design and Synthesis of Macrocyclic Compounds)
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