One-Pot Route to X-perfluoroarenes (X = Br, I) Based on FeIII-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

2020 ◽  
Vol 20 (9) ◽  
pp. 5908-5921 ◽  
Author(s):  
Anton V. Rozhkov ◽  
Anastasiya A. Eliseeva ◽  
Sergey V. Baykov ◽  
Bartomeu Galmés ◽  
Antonio Frontera ◽  
...  
Keyword(s):  
Crystal Engineering ◽  
Halogen Bonding ◽  
Building Blocks ◽  
One Pot

scholarly journals Direct and Telescopic Mechanochemical Synthesis of Higher-order Organic-Inorganic Hybrid Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design

2021 ◽  
Author(s):  
Zi xuan Ng ◽  
Davin Tan ◽  
Wei Liang Teo ◽  
felix leon ◽  
Xiaoyan Shi ◽  
...  
Keyword(s):  
Mechanochemical Synthesis ◽  
Crystal Engineering ◽  
Computational Modelling ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Intermolecular Forces ◽  
Higher Order ◽  
The Novel ◽  
Engineering Research ◽  
Dipole Interactions

The ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research over the past two decades. When building higher-order multicomponent cocrystals (i.e. crystals containing more than two constituents), the differential and hierarchical way molecules interact and assemble in the solidstate is of pinnacle importance. To date, numerous examples of multicomponent crystals comprising organic molecules leading to salts, cocrystals or ionic cocrystals have been reported. However, the crystal engineering of hybrid organicinorganic cocrystals with sophisticated inorganic building blocks is still poorly understood and mostly unexplored. Here, we reveal the first efficient mechanochemical synthesis of higher-order hybrid organic-inorganic cocrystals based on the structurally versatile – yet largely unexplored – cyclodiphos(V/V)azane heterosynthon building block. The novel hybrid ternary and quaternary multicomponent cocrystals herein reported are held together by synergistic intermolecular interactions (e.g., hydrogen- and halogen-bonding, Se-π and ion-dipole interactions). Notably, higher-order ternary and quaternary cocrystals can be readily obtained either via direct synthetic routes from its individual components, or via unprecedented telescopic approaches from lower-order cocrystal sets. In addition, computational modelling has also revealed that the formation of higher-order cocrystals is thermodynamically driven, and that bulk moduli and compressibilities are strongly dependent on the chemical composition and intermolecular forces present in the crystals, which offer untapped potential for optimizing material properties.

scholarly journals Direct and Telescopic Mechanochemical Synthesis of Higher-order Organic-Inorganic Hybrid Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design

2021 ◽  
Author(s):  
Zi xuan Ng ◽  
Davin Tan ◽  
Wei Liang Teo ◽  
felix leon ◽  
Xiaoyan Shi ◽  
...  
Keyword(s):  
Mechanochemical Synthesis ◽  
Crystal Engineering ◽  
Computational Modelling ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Intermolecular Forces ◽  
Higher Order ◽  
The Novel ◽  
Engineering Research ◽  
Dipole Interactions

The ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research over the past two decades. When building higher-order multicomponent cocrystals (i.e. crystals containing more than two constituents), the differential and hierarchical way molecules interact and assemble in the solidstate is of pinnacle importance. To date, numerous examples of multicomponent crystals comprising organic molecules leading to salts, cocrystals or ionic cocrystals have been reported. However, the crystal engineering of hybrid organicinorganic cocrystals with sophisticated inorganic building blocks is still poorly understood and mostly unexplored. Here, we reveal the first efficient mechanochemical synthesis of higher-order hybrid organic-inorganic cocrystals based on the structurally versatile – yet largely unexplored – cyclodiphos(V/V)azane heterosynthon building block. The novel hybrid ternary and quaternary multicomponent cocrystals herein reported are held together by synergistic intermolecular interactions (e.g., hydrogen- and halogen-bonding, Se-π and ion-dipole interactions). Notably, higher-order ternary and quaternary cocrystals can be readily obtained either via direct synthetic routes from its individual components, or via unprecedented telescopic approaches from lower-order cocrystal sets. In addition, computational modelling has also revealed that the formation of higher-order cocrystals is thermodynamically driven, and that bulk moduli and compressibilities are strongly dependent on the chemical composition and intermolecular forces present in the crystals, which offer untapped potential for optimizing material properties.

Synthesis of Nitrile-Bearing Quaternary Centers via an Equilibrium-Driven Transnitrilation and Anion-Relay Strategy

2019 ◽  
Author(s):  
Sebastien Alazet ◽  
Michael West ◽  
Purvish Patel ◽  
Sophie Rousseaux
Keyword(s):  
Building Blocks ◽  
One Pot ◽  
Quaternary Centers ◽  
Synthetic Intermediates

The efficient preparation of nitrile-containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals. As a result, significant efforts have been made to develop methods to access these motifs which rely on safer and non-toxic sources of CN. Herein, we report that 2-methyl-2-phenylpropanenitrile is an efficient, non-toxic, electrophilic CN source for the synthesis of nitrile-bearing quaternary centers via a thermodynamic transnitrilation and anion-relay strategy. This one-pot process leads to nitrile products resulting from the gem-difunctionalization of alkyl lithium reagents.<br>

scholarly journals 2-Aryl-6-Polyfluoroalkyl-4-Pyrones as Promising RF-Building-Blocks: Synthesis and Application for Construction of Fluorinated Azaheterocycles

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4415
Author(s):  
Sergey A. Usachev ◽  
Diana I. Nigamatova ◽  
Daria K. Mysik ◽  
Nikita A. Naumov ◽  
Dmitrii L. Obydennov ◽  
...  
Keyword(s):  
Direct Synthesis ◽  
Building Blocks ◽  
Oxidative Cyclization ◽  
One Pot ◽  
Synthetic Application ◽  
General Method

A convenient and general method for the direct synthesis of 2-aryl-6-(trifluoromethyl)-4-pyrones and 2-aryl-5-bromo-6-(trifluoromethyl)-4-pyrones has been developed on the basis of one-pot oxidative cyclization of (E)-6-aryl-1,1,1-trifluorohex-5-ene-2,4-diones via a bromination/dehydrobromination approach. This strategy was also applied for the preparation of 2-phenyl-6-polyfluoroalkyl-4-pyrones and their 5-bromo derivatives. Conditions of chemoselective enediones bromination were found and the key intermediates of the cyclization of bromo-derivatives to 4-pyrones were characterized. Synthetic application of the prepared 4-pyrones has been demonstrated for the construction of biologically important CF3-bearing azaheterocycles, such as pyrazoles, pyridones, and triazoles.

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.

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.

Access to Unnatural Glycosyl Amino Acid Building Blocks via a One-Pot Ritter Reaction

Synlett ◽  
2005 ◽  
pp. 212-216 ◽  
Author(s):  
Frank Schweizer ◽  
Marlin Penner ◽  
David Taylor ◽  
Danielle Desautels ◽  
Kirk Marat
Keyword(s):  
Amino Acid ◽  
Building Blocks ◽  
Ritter Reaction ◽  
One Pot

Hierarchy of Supramolecular Arrangements and Building Blocks: Inverted Paradigm of Crystal Engineering in the Unprecedented Metal Coordination of Methylene Blue

2017 ◽  
Vol 56 (6) ◽  
pp. 3512-3516 ◽  
Author(s):  
Stefano Canossa ◽  
Alessia Bacchi ◽  
Claudia Graiff ◽  
Paolo Pelagatti ◽  
Giovanni Predieri ◽  
...  
Keyword(s):  
Methylene Blue ◽  
Crystal Engineering ◽  
Building Blocks ◽  
Metal Coordination ◽  
Supramolecular Arrangements

Symmetrical tetra-β″-sulfoleno-meso-aryl-porphyrins — synthesis, spectroscopy and structural characterization

2014 ◽  
Vol 18 (01n02) ◽  
pp. 115-122 ◽  
Author(s):  
Srinivas Banala ◽  
Klaus Wurst ◽  
Bernhard Kräutler
Keyword(s):  
Metal Complexes ◽  
Crystal Structures ◽  
Structural Characterization ◽  
Building Blocks ◽  
Cycloaddition Reactions ◽  
One Pot

We report here the preparation (in "one-pot") of a tetra-β″-sulfoleno-meso-aryl-porphyrin in about 80% yield by using an optimized modification of Lindsey's variant of the Adler–Longo approach. The Zn ( II )-, Cu ( II )- and Ni ( II )-complexes of the symmetrical porphyrin were prepared and characterized spectroscopically. Crystal structures of the fluorescent Zn ( II )- and of the non-fluorescent Ni ( II )-tetra-β″-sulfoleno-meso-aryl-porphyrinates showed the highly substituted porphyrin ligands to be nearly perfectly planar. The Zn ( II )-complex of this porphyrin has been used as a thermal precursor of a reactive diene, and — formally — of lateral and diagonal bis-dienes, of a tris-diene and of a tetra-diene, which all underwent [4 + 2]-cycloaddition reactions in situ with a range of dienophiles. Thus, the tetra-β″-sulfoleno-meso-aryl-porphyrin and its metal complexes represent reactive building blocks, "programmed" for the syntheses of symmetrical and highly functionalized porphyrins.

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