A Molecular Building-Block Approach to the Synthesis of Ceramic Materials

1986 ◽  
Vol 73 ◽  
Author(s):  
W. G. Klemperer ◽  
V. V. Mainz ◽  
D. M. Millar
Keyword(s):  
Molecular Level ◽  
Building Blocks ◽  
Ceramic Materials ◽  
Polysilicic Acid ◽  
Molecular Building Block ◽  
Molecular Building Blocks ◽  
Subsequent Step ◽  
Solution Nuclear Magnetic Resonance ◽  
Acid Esters ◽  
Block Approach

ABSTRACTCeramic materials are generally prepared from structurally simple starting materials, with the consequence that structural properties are difficult to control on a molecular level. This difficulty might be addressed by following the approach taken in polymer chemistry in which molecular building blocks are first prepared and then polymerized in a subsequent step. In the present case, the polysilicic acid esters [Si2O](OCH3)6, [Si3O2](OCH3)8, and [Si8O12](OCH3)8 are prepared and then polymerized by hydrolysis/condensation. Silicon-29 solution nuclear magnetic resonance (NMR) spectroscopy is used to estimate the extent to which the molecular frameworks of these monomers are retained during the course of hydrolysis and condensation.

scholarly journals Intrinsically porous molecular building blocks for metal organic frameworks tailored by the bridging effect of counter cations

CrystEngComm ◽  
2020 ◽  
Vol 22 (17) ◽  
pp. 2889-2894 ◽  
Author(s):  
Peng Yang ◽  
Buthainah Alshankiti ◽  
Niveen M. Khashab
Keyword(s):  
Porous Materials ◽  
Rational Design ◽  
Molecular Level ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Molecular Building Blocks ◽  
Metal Organic ◽  
Design And Construction

Intrinsically porous molecular building blocks are used for the rational design and construction of molecular-level controlled porous materials.

scholarly journals Engineering Micromechanics of Soft Porous Crystals for Negative Gas Adsorption

2020 ◽  
Author(s):  
Simon Krause ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Irena Senkovska ◽  
Sebastian Ehrling ◽  
...  
Keyword(s):  
Yield Stress ◽  
Mechanical Response ◽  
Gas Adsorption ◽  
Molecular Level ◽  
Nitrogen Adsorption ◽  
Building Blocks ◽  
Activation Barriers ◽  
Framework Materials ◽  
Dynamic Framework ◽  
Molecular Building Blocks

Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks’ 30 mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the 31 molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases elasticity, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the 36 activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol–1 37 per unit cell, and moderate yield stress of 0.6 to 38 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials<br>

scholarly journals Engineering Micromechanics of Soft Porous Crystals for Negative Gas Adsorption

2020 ◽  
Author(s):  
Simon Krause ◽  
Jack D. Evans ◽  
Volodymyr Bon ◽  
Irena Senkovska ◽  
Sebastian Ehrling ◽  
...  
Keyword(s):  
Yield Stress ◽  
Mechanical Response ◽  
Gas Adsorption ◽  
Molecular Level ◽  
Nitrogen Adsorption ◽  
Building Blocks ◽  
Activation Barriers ◽  
Framework Materials ◽  
Dynamic Framework ◽  
Molecular Building Blocks

Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks’ 30 mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the 31 molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases elasticity, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the 36 activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol–1 37 per unit cell, and moderate yield stress of 0.6 to 38 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials<br>

Molecular building blocks for the synthesis of ceramic materials: [Si8O12](OCH3)8

1985 ◽  
Vol 107 (26) ◽  
pp. 8262-8264 ◽  
Author(s):  
V. W. Day ◽  
Walter G. Klemperer ◽  
V. V. Mainz ◽  
D. M. Millar
Keyword(s):  
Building Blocks ◽  
Ceramic Materials ◽  
Molecular Building Blocks

A First Principles Approach for Partitioning Linear Response Properties into Additive and Cooperative Contributions

2018 ◽  
Author(s):  
Daniel Lambrecht ◽  
Eric Berquist
Keyword(s):  
First Principles ◽  
Linear Response ◽  
Building Blocks ◽  
Field Method ◽  
Response Property ◽  
Response Properties ◽  
Consistent Field ◽  
Molecular Building Blocks ◽  
Self Consistent ◽  
Self Consistent Field

We present a first principles approach for decomposing molecular linear response properties into orthogonal (additive) plus non-orthogonal/cooperative contributions. This approach enables one to 1) identify the contributions of molecular building blocks like functional groups or monomer units to a given response property and 2) quantify cooperativity between these contributions. In analogy to the self consistent field method for molecular interactions, SCF(MI), we term our approach LR(MI). The theory, implementation and pilot data are described in detail in the manuscript and supporting information.

Stress-responsive properties of metallocenes in metallopolymers

2021 ◽  
Author(s):  
Ye Sha ◽  
Hao Zhang ◽  
Zhou Zhou ◽  
Zhenyang Luo
Keyword(s):  
Molecular Level ◽  
Building Blocks ◽  
Review Article ◽  
Stress Responsiveness

This review article combines the field of metallopolymers and stress-responsiveness on a molecular level, namely, metallocenes, as emerging stress-responsive building blocks for materials.

A new molecular building blocks: Synthesis, crystal structure, magnetic and spectroscopic properties of Cu(II) and Ni(II) macrocyclic complexes

Polyhedron ◽  
2011 ◽  
Vol 30 (15) ◽  
pp. 2550-2557 ◽  
Author(s):  
Katarzyna Suracka ◽  
Alina Bieńko ◽  
Jerzy Mroziński ◽  
Rafał Kruszyński ◽  
Dariusz Bieńko ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Building Blocks ◽  
Spectroscopic Properties ◽  
Macrocyclic Complexes ◽  
Molecular Building Blocks

scholarly journals Acid-Catalysed Liquid-to-Solid Transitioning of Arylazoisoxazole Photoswitches

2021 ◽  
Author(s):  
Luuk Kortekaas ◽  
Julian Simke ◽  
Niklas Arndt ◽  
Marcus Böckmann ◽  
Nikos Doltsinis ◽  
...  
Keyword(s):  
Building Blocks ◽  
Vital Role ◽  
Responsive Materials ◽  
Molecular Building Blocks ◽  
Physical Changes

Molecular photoswitches play a vital role in the development of responsive materials. These molecular building blocks are particularly attractive when multiple stimuli can be combined to bring about physical changes,...

A Molecular Artisans Guide to Supramolecular Coordination Complexes and Metal Organic Frameworks

2015 ◽  
Vol 03 (01n02) ◽  
pp. 1540004 ◽  
Author(s):  
Xialu Wu ◽  
David J. Young ◽  
T. S. Andy Hor
Keyword(s):  
Chemical Reactivity ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Coordination Complexes ◽  
Large Molecules ◽  
Molecular Building Blocks ◽  
Supramolecular Coordination ◽  
Metal Organic ◽  
Molecular Synthesis ◽  
And Function

As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.

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