Metal Cyamelurates: Structural Diversity Caused by Kinetic and Thermodynamic Controls

Abstract The kinetic control of chemical reactions makes it possible both to isolate metastable substances with properties different from those of thermodynamically stable phases, and to obtain information useful for studying the crystal nucleation and further transformations of metastable phases into stable ones. Metal cyamelurates are suitable subjects for kinetic control in synthesis due to their easy crystallization and short reaction times. In this work cobalt, manganese, magnesium, copper, aluminum, chromium, calcium and lead cyamelurates were obtained and their crystal structures were determined. Most syntheses at room temperature take place under kinetic control, and this often leads to a mixture of phases. KM(C6N7O3)·5H2O (M=Co(II), Mn(II)) powders consisted of one crystalline compound. An increase in temperature leads to thermodynamic control, which is proved by registration of Mn(C6N7O3H)·5H2O and KMg(C6N7O3)·5H2O crystalline phases. It was possible to isolate Ca(C6 N7O3H)·6H2O and Pb(C6N7O3H)·3H2O from the mixture by washing samples with a weak acid solution. As a result of the work, five different structural types were obtained, including KCu(C6N7O3)∙2H2O and KM(C6N7O3H) 2 ·6H2O (M=Al, Cr(III)). Despite the diversity of salts obtained as a result of thermodynamic or kinetic control, practically the same building blocks form the crystal structure of cyamelurates. The hypothesis of nucleation in a colloidal micelle with electric double layer can be applied to the compounds listed above.

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1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

Molecules ◽

10.3390/molecules26051214 ◽

2021 ◽

Vol 26 (5) ◽

pp. 1214

Author(s):

Sergey N. Podyachev ◽

Rustem R. Zairov ◽

Asiya R. Mustafina

Keyword(s):

Structural Diversity ◽

Building Blocks ◽

Structural Features ◽

Structure Property ◽

One Pot ◽

Arene Ligands ◽

Structure Property Relationships ◽

New Type ◽

Synthetic Routes ◽

Magnetic Resonance Imaging Mri

The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure–property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging.

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Glycosylation under Thermodynamic Control: Synthesis of the Di- and the Hexasaccharide Fragments of the O-SP ofVibrio Cholerae O:1 Serotype Ogawa from Fully Functionalized Building Blocks

European Journal of Organic Chemistry ◽

10.1002/ejoc.200600851 ◽

2007 ◽

Vol 2007 (6) ◽

pp. 988-1000 ◽

Cited By ~ 10

Author(s):

Roberto Adamo ◽

Pavol Kováč

Keyword(s):

Building Blocks ◽

Control Synthesis ◽

Thermodynamic Control

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Functional phosphorus-based π-conjugated systems: Structural diversity without multistep synthesis

Pure and Applied Chemistry ◽

10.1351/pac200779020201 ◽

2007 ◽

Vol 79 (2) ◽

pp. 201-212 ◽

Cited By ~ 24

Author(s):

Muriel Hissler ◽

Christophe Lescop ◽

Régis Réau

Keyword(s):

Structural Diversity ◽

Building Blocks ◽

Transition Metal Ions ◽

Organic Light Emitting Diodes ◽

Supramolecular Organization ◽

Chemical Transformations ◽

Light Emitting ◽

Conjugated Systems ◽

Multistep Synthesis ◽

Organic Light

The synthesis and properties of linear π-conjugated systems incorporating phosphole rings are described. Their supramolecular organization in the solid state can be controlled either by chemical modifications or coordination to transition metals of the phosphorus atom. Furthermore, chemical transformations of the phosphole ring allow organizing these P-chromophores in 3D assemblies exhibiting σ-π conjugation or in organometallic ferrocene-like derivatives. Phosphole-pyridine-containing π-conjugated chromophores act as P,N-chelates toward transition-metal ions, giving rise to mono- and di-nuclear complexes. The specific properties of these complexes make them valuable materials for organic light-emitting diodes (OLEDs) and interesting building blocks for the tailoring of π-conjugated systems.

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2-Pyridyl Tosylate Derivatives-Building Blocks for Structural Diversity via Transition Metal Catalysis

Israel Journal of Chemistry ◽

10.1002/ijch.201000031 ◽

2010 ◽

Vol 50 (5-6) ◽

pp. 558-567 ◽

Cited By ~ 7

Author(s):

Anders T. Lindhardt ◽

Thomas M. Gøgsig ◽

Delphine Gauthier ◽

Daniel Lupp ◽

Mette Louise Hallager Mantel ◽

...

Keyword(s):

Transition Metal ◽

Structural Diversity ◽

Building Blocks ◽

Transition Metal Catalysis ◽

Metal Catalysis

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Cover Picture: Exploring and Expanding the Structural Diversity of Self-Assembling Dendrons through Combinations of AB, Constitutional Isomeric AB2, and AB3 Biphenyl-4-Methyl Ether Building Blocks (Chem. Eur. J. 24/2006)

Chemistry - A European Journal ◽

10.1002/chem.200690075 ◽

2006 ◽

Vol 12 (24) ◽

pp. 6183-6183

Author(s):

Virgil Percec ◽

Marian N. Holerca ◽

Sami Nummelin ◽

John J. Morrison ◽

Martin Glodde ◽

...

Keyword(s):

Methyl Ether ◽

Structural Diversity ◽

Building Blocks ◽

Self Assembling ◽

J 24

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Experimental and Theoretical Investigation of the Reaction of Secondary Amines with Maleic Anhydride

Australian Journal of Chemistry ◽

10.1071/ch17206 ◽

2017 ◽

Vol 70 (12) ◽

pp. 1247 ◽

Cited By ~ 3

Author(s):

Manjinder Kour ◽

Raakhi Gupta ◽

Raj K. Bansal

Keyword(s):

Maleic Anhydride ◽

Carbonyl Group ◽

Carbonyl Compounds ◽

Secondary Amines ◽

Kinetic Control ◽

Thermodynamic Control ◽

Carbonyl Carbon ◽

Fukui Functions ◽

Unsaturated Carbonyl Compound ◽

Condensed Fukui Functions

The reaction of secondary amines, namely 1-methylpiperazine, pyrrolidine, morpholine, 2-methylpiperidine, and diethylamine, with maleic anhydride has been investigated experimentally and theoretically at the DFT level. Under kinetic control, i.e. at −78°C or −15°C, amines add across the C=O functionality exclusively and the initially formed addition products isomerize to the corresponding N-substituted maleimic acid derivatives. In contrast to the acyclic α,β-unsaturated carbonyl compounds, amine does not add across the C=C functionality in maleic anhydride even under thermodynamic control. This behaviour of maleic anhydride can be rationalized on the basis of the local condensed Fukui functions, which reveal that the carbonyl carbon atoms in maleic anhydride are much harder than in an acyclic α,β-unsaturated carbonyl compound, such as acrolein. This prompts the amines to attack the carbonyl group in maleic anhydride exclusively.

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Unusual Two-Dimensional Nickel(II) Complexes Based on [Ni(dien)]2+ and [M(CN)4]2− Building Blocks (M = Ni, Pd and Pt)− Synthesis, Structural Diversity and Magnetic Properties

European Journal of Inorganic Chemistry ◽

10.1002/ejic.200300696 ◽

2004 ◽

Vol 2004 (9) ◽

pp. 1886-1893 ◽

Cited By ~ 26

Author(s):

Iñaki Muga ◽

Juan M. Gutiérrez-Zorrilla ◽

Pablo Vitoria ◽

Pascual Román ◽

Luis Lezama ◽

...

Keyword(s):

Magnetic Properties ◽

Structural Diversity ◽

Building Blocks ◽

Two Dimensional

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Helicity control in the synthesis of helicenes and related compounds

Pure and Applied Chemistry ◽

10.1351/pac200678020495 ◽

2006 ◽

Vol 78 (2) ◽

pp. 495-499 ◽

Cited By ~ 37

Author(s):

Ivo Starý ◽

Irena G. Stará ◽

Zuzana Alexandrová ◽

Petr Sehnal ◽

Filip Teplý ◽

...

Keyword(s):

Asymmetric Synthesis ◽

Kinetic Control ◽

Thermodynamic Control ◽

Further Development ◽

Related Compounds

Asymmetric synthesis of helicenes and their congeners has been demonstrated to rely either on enantioselective Ni0/PR3*-catalyzed [2+2+2] cycloisomerization of triynes or on diastereoselective CoI-catalyzed [2+2+2] cycloisomerization of chiral triynes. The former approach providing tetrahydrohelicenes in a nonracemic form requires further development as moderate enantioselectivities (up to 54 % ee) have so far been achieved under kinetic control. The latter approach affording helicene-like structures in a diastereomerically enriched form allows for reaching good to excellent diastereoselectivities (up to 100:0) under thermodynamic control.

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