Comparison of halogen bonding networks with Ru(ii) complexes and analysis of the influence of the XB interactions on their reactivity

2017 ◽  
Vol 203 ◽  
pp. 257-283 ◽  
Author(s):  
Marta E. G. Mosquera ◽  
Irene Egido ◽  
Carlos Hortelano ◽  
María López-López ◽  
Pilar Gómez-Sal
Keyword(s):  
Coordination Compounds ◽  
Analogous Result ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Structural Features ◽  
Isocyanide Ligands ◽  
Unexpected Reaction ◽  
Chloride Ligand ◽  
Chloride Ligands ◽  
Supramolecular Networks

Coordination compounds of formula [Ru(Cl)2(CNR)4] are interesting building blocks for the preparation of halogen bonding supramolecular networks, since the chloride ligand is a good XB acceptor. When using I2 as the XB donor, an unexpected reaction on the ruthenium coordination sphere happens where the chloride ligands are substituted by iodides. The isolation of several intermediates with different substitution degrees and showing XB interactions in a solid state network evidenced the clear influence of the XB species in this unusual reaction process. The extension of the studies to bromine gave the analogous result, i.e. the substitution of the chloride ligands by bromides. Furthermore, changing the organic substituent in the isocyanide ligands from alkyl to aryl does not affect the outcome of the reaction; however the process is faster when the alkyl substituents are present. In the course of the study of these reactions we have isolated a whole range of XB-based networks were interactions such as Cl⋯I–I, Br⋯Br–Br, I⋯I–I and I⋯Br–Br are present, a systematic comparison of the XB structural features for the different networks isolated and the influence in their reactivity has been performed.

A variety of metal–organic and supramolecular networks constructed from a new flexible multifunctional building block bearing picolinate and terephthalate functionalities: hydrothermal self-assembly, structural features, magnetic and luminescent properties

RSC Advances ◽  
2015 ◽  
Vol 5 (106) ◽  
pp. 87484-87495 ◽  
Author(s):  
Yong-Liang Shao ◽  
Yan-Hui Cui ◽  
Jin-Zhong Gu ◽  
Alexander M. Kirillov ◽  
Jiang Wu ◽  
...  
Keyword(s):  
Self Assembly ◽  
Building Block ◽  
Coordination Compounds ◽  
Luminescent Properties ◽  
Structural Features ◽  
Metal Organic ◽  
Supramolecular Networks

A novel multifunctional building block was designed and applied for the synthesis of diverse coordination compounds.

Self-assembly generation, structural features, and oxidation catalytic properties of new aqua-soluble copper(ii)-aminoalcohol derivatives

2017 ◽  
Vol 4 (6) ◽  
pp. 968-977 ◽  
Author(s):  
Marina V. Kirillova ◽  
Carla I. M. Santos ◽  
Vânia André ◽  
Tiago A. Fernandes ◽  
Sara S. P. Dias ◽  
...  
Keyword(s):  
Self Assembly ◽  
Coordination Compounds ◽  
Catalytic Properties ◽  
Building Blocks ◽  
Structural Features ◽  
Free Oxidation

Multidentate aminoalcohols were applied as unexplored building blocks to generate two novel Cu(ii) coordination compounds that act as efficient catalysts for the mild and acid-promoter-free oxidation of C5–C8 cycloalkanes.

Interplay between H-bonding and interpenetration in an aqueous copper(ii)–aminoalcohol–pyromellitic acid system: self-assembly synthesis, structural features and catalysis

2018 ◽  
Vol 47 (46) ◽  
pp. 16674-16683 ◽  
Author(s):  
Tiago A. Fernandes ◽  
Marina V. Kirillova ◽  
Vânia André ◽  
Alexander M. Kirillov
Keyword(s):  
Self Assembly ◽  
Coordination Compounds ◽  
Building Blocks ◽  
Structural Features ◽  
Acid System ◽  
Pyromellitic Acid ◽  
Self Assembled

Two new copper(ii) coordination compounds were self-assembled from N-methyldiethanolamine and pyromellitic acid as principal building blocks; their structural and catalytic features were investigated.

A Pseudo Five-Fold Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen Bonded Frameworks

2020 ◽  
Author(s):  
Frederik Haase ◽  
Gavin Craig ◽  
Mickaele Bonneau ◽  
kunihisa sugimoto ◽  
Shuhei Furukawa
Keyword(s):  
Topological Defects ◽  
Porous Metal ◽  
Building Blocks ◽  
Structural Features ◽  
Equilibrium Structure ◽  
Sorption Behavior ◽  
Building Unit ◽  
Geometric Frustration ◽  
Secondary Building Units ◽  
Hydrogen Bonded

Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining “incompatible” building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo C<sub>5</sub> symmetrical organic building unit based on a pyrrole core, with a C<sub>4</sub> symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures and topological defects in the equilibrium structure, which manifested in the formation of a hydrogen bonded framework, distorted and broken secondary building units and dangling functional groups, respectively. The influence of geometric frustration on the CO<sub>2</sub> sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.

A Pseudo Five-Fold Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen Bonded Frameworks

2020 ◽  
Author(s):  
Frederik Haase ◽  
Gavin Craig ◽  
Mickaele Bonneau ◽  
kunihisa sugimoto ◽  
Shuhei Furukawa
Keyword(s):  
Topological Defects ◽  
Porous Metal ◽  
Building Blocks ◽  
Structural Features ◽  
Equilibrium Structure ◽  
Sorption Behavior ◽  
Building Unit ◽  
Geometric Frustration ◽  
Secondary Building Units ◽  
Hydrogen Bonded

Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining “incompatible” building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo C<sub>5</sub> symmetrical organic building unit based on a pyrrole core, with a C<sub>4</sub> symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures and topological defects in the equilibrium structure, which manifested in the formation of a hydrogen bonded framework, distorted and broken secondary building units and dangling functional groups, respectively. The influence of geometric frustration on the CO<sub>2</sub> sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.

Application of Nitrogen Heterocyclic Carbenes in Organocatalysis

2020 ◽  
Vol 09 ◽  
Author(s):  
Minita Ojha ◽  
R. K. Bansal
Keyword(s):  
Asymmetric Catalysis ◽  
Building Blocks ◽  
Structural Features ◽  
Heterocyclic Carbenes ◽  
Stetter Reaction ◽  
Metal Pollutants ◽  
Synthetic Strategy ◽  
Wide Range ◽  
Benzoin Condensation ◽  
Nitrogen Heterocyclic

Background: During the last two decades, horizon of research in the field of Nitrogen Heterocyclic Carbenes (NHC) has widened remarkably. NHCs have emerged as ubiquitous species having applications in a broad range of fields, including organocatalysis and organometallic chemistry. The NHC-induced non-asymmetric catalysis has turned out to be a really fruitful area of research in recent years. Methods: By manipulating structural features and selecting appropriate substituent groups, it has been possible to control the kinetic and thermodynamic stability of a wide range of NHCs, which can be tolerant to a variety of functional groups and can be used under mild conditions. NHCs are produced by different methods, such as deprotonation of Nalkylhetrocyclic salt, transmetallation, decarboxylation and electrochemical reduction. Results: The NHCs have been used successfully as catalysts for a wide range of reactions making a large number of building blocks and other useful compounds accessible. Some of these reactions are: benzoin condensation, Stetter reaction, Michael reaction, esterification, activation of esters, activation of isocyanides, polymerization, different cycloaddition reactions, isomerization, etc. The present review includes all these examples published during the last 10 years, i.e. from 2010 till date. Conclusion: The NHCs have emerged as versatile and powerful organocatalysts in synthetic organic chemistry. They provide the synthetic strategy which does not burden the environment with metal pollutants and thus fit in the Green Chemistry.

scholarly journals Copper(II) 2,2-Bis(Hydroxymethyl)Propionate Coordination Compounds with Hexamethylenetetramine: From Mononuclear Complex to One-Dimensional Coordination Polymer

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3358
Author(s):  
Sadaf Rauf ◽  
Agata Trzesowska-Kruszynska ◽  
Tomasz Sierański ◽  
Marcin Świątkowski
Keyword(s):  
Coordination Polymer ◽  
Coordination Compounds ◽  
Structural Diversity ◽  
Structural Features ◽  
Mononuclear Complex ◽  
Molar Ratio ◽  
One Dimensional ◽  
1D Coordination Polymer ◽  
Copper Coordination ◽  
Stretching Vibrations

Three new copper coordination compounds derived from 2,2-bis(hydroxymethyl)propionic acid (dmpa) and hexamethylenetetramine (hmta) were obtained and their crystal structures were determined. The stoichiometry of the reagents applied in the syntheses reflects the metal to ligand molar ratio in the formed solid products. Due to the multiple coordination modes of the used ligands, wide structural diversity was achieved among synthesized compounds, i.e., mononuclear [Cu(dmp)2(hmta)2(H2O)] (1), dinuclear [Cu2(dmp)4(hmta)2] (2), and 1D coordination polymer [Cu2(dmp)4(hmta)]n (3). Their supramolecular structures are governed by O—H•••O and O—H•••N hydrogen bonds. The compounds were characterized in terms of absorption (UV-Vis and IR) and thermal properties. The relationships between structural features and properties were discussed in detail. Owing to discrepancies in the coordination mode of a dmp ligand, bidentate chelating in 1, and bidentate bridging in 2 and 3, there is a noticeable change in the position of the bands corresponding to the stretching vibrations of the carboxylate group in the IR spectra. The differences in the structures of the compounds are also reflected in the nature and position of the UV-Vis absorption maxima, which are located at lower wavelengths for 1.

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

Molecules ◽  
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.

H-Bonded and metal(ii)–organic architectures assembled from an unexplored aromatic tricarboxylic acid: structural variety and functional properties

2020 ◽  
Vol 49 (21) ◽  
pp. 7197-7209 ◽  
Author(s):  
Jin-Zhong Gu ◽  
Shi-Mao Wan ◽  
Marina V. Kirillova ◽  
Alexander M. Kirillov
Keyword(s):  
Nicotinic Acid ◽  
Functional Properties ◽  
Building Block ◽  
Coordination Compounds ◽  
Structural Features ◽  
Tricarboxylic Acid ◽  
Structural Variety

2,5-Di(4-carboxylphenyl)nicotinic acid was explored as a novel building block for assembling nine metal(ii) coordination compounds; these were fully characterized and their structural features and functional properties were investigated.

scholarly journals Fluorinated azobenzenes as supramolecular halogen-bonding building blocks

2019 ◽  
Vol 15 ◽  
pp. 2013-2019 ◽  
Author(s):  
Esther Nieland ◽  
Oliver Weingart ◽  
Bernd M Schmidt
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Visible Light ◽  
Half Life ◽  
Photophysical Properties ◽  
Bathochromic Shift ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Partial Overlap

ortho-Fluoroazobenzenes are a remarkable example of bistable photoswitches, addressable by visible light. Symmetrical, highly fluorinated azobenzenes bearing an iodine substituent in para-position were shown to be suitable supramolecular building blocks both in solution and in the solid state in combination with neutral halogen bonding acceptors, such as lutidines. Therefore, we investigate the photochemistry of a series of azobenzene photoswitches. Upon introduction of iodoethynyl groups, the halogen bonding donor properties are significantly strengthened in solution. However, the bathochromic shift of the π→π* band leads to a partial overlap with the n→π* band, making it slightly more difficult to address. The introduction of iodine substituents is furthermore accompanied with a diminishing thermal half-life. A series of three azobenzenes with different halogen bonding donor properties are discussed in relation to their changing photophysical properties, rationalized by DFT calculations.

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