What is the driving force behind molecular triangles and their guests? A quantum chemical perspective about host–guest interactions

2020 ◽  
Vol 22 (34) ◽  
pp. 19213-19222 ◽  
Author(s):  
Glaucio R. Nagurniak ◽  
Maurício J. Piotrowski ◽  
Àlvaro Muñoz-Castro ◽  
João B. S. Cascaldi ◽  
Renato L. T. Parreira ◽  
...  
Keyword(s):  
Chemical Shift ◽  
Dft Calculations ◽  
Quantum Chemical ◽  
Driving Force ◽  
Physical Nature ◽  
Energy Decomposition ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Nuclear Independent Chemical Shift

The physical nature of host–guest interactions occurring between molecular triangles and linear anions was explored using DFT calculations combined with energy decomposition analyses, nuclear independent chemical shift, and non-covalent interactions.

scholarly journals Strength and Nature of Host-Guest Interactions in Metal-Organic Frameworks from a Quantum-Chemical Perspective

2021 ◽  
Author(s):  
Michelle Enst ◽  
Ganna Gryn'ova
Keyword(s):  
Density Functional Theory ◽  
Quantum Chemical ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Energy Decomposition ◽  
Functional Theory ◽  
Metal Organic ◽  
Non Covalent Interactions ◽  
Decomposition Schemes ◽  
Covalent Interactions

<div> <div> <div> <p>Metal-organic frameworks offer a convenient means for capturing, transporting, and releasing small molecules. Rational design of such systems requires an in-depth understanding of the underlying non-covalent interactions, and the ability to easily and rapidly pre-screen candidate architectures in silico. In this work, we devised a recipe for computing the strength and analysing the nature of the host-guest interactions in MOFs. Using experimentally characterised complexes of calcium-adipate framework with 4,4’-bipyridine and 1,2-bis(4-pyridyl)ethane guests as test systems, we have assessed a range of density functional theory methods, energy decomposition schemes, and non-covalent interactions indicators across realistic periodic and finite supramolecular cluster scales. We find that appropriately constructed clusters readily reproduce the key interactions occurring in periodic models at a fraction of the computational cost and with an added benefit of diverse density partitioning schemes. Host-guest interaction energies can be reliably computed with dispersion- corrected density functional theory methods; however, decoding their precise nature demands insights from energy decomposition schemes and quantum-chemical tools beyond local bonding indices (e.g., the quantum theory of atoms in molecules), such as the non-covalent interactions index and the density overlap regions indicator. </p> </div> </div> </div>

scholarly journals Strength and Nature of Host-Guest Interactions in Metal-Organic Frameworks from a Quantum-Chemical Perspective

2021 ◽  
Author(s):  
Michelle Enst ◽  
Ganna Gryn'ova
Keyword(s):  
Density Functional Theory ◽  
Quantum Chemical ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Energy Decomposition ◽  
Functional Theory ◽  
Metal Organic ◽  
Non Covalent Interactions ◽  
Decomposition Schemes ◽  
Covalent Interactions

<div> <div> <div> <p>Metal-organic frameworks offer a convenient means for capturing, transporting, and releasing small molecules. Rational design of such systems requires an in-depth understanding of the underlying non-covalent interactions, and the ability to easily and rapidly pre-screen candidate architectures in silico. In this work, we devised a recipe for computing the strength and analysing the nature of the host-guest interactions in MOFs. Using experimentally characterised complexes of calcium-adipate framework with 4,4’-bipyridine and 1,2-bis(4-pyridyl)ethane guests as test systems, we have assessed a range of density functional theory methods, energy decomposition schemes, and non-covalent interactions indicators across realistic periodic and finite supramolecular cluster scales. We find that appropriately constructed clusters readily reproduce the key interactions occurring in periodic models at a fraction of the computational cost and with an added benefit of diverse density partitioning schemes. Host-guest interaction energies can be reliably computed with dispersion- corrected density functional theory methods; however, decoding their precise nature demands insights from energy decomposition schemes and quantum-chemical tools beyond local bonding indices (e.g., the quantum theory of atoms in molecules), such as the non-covalent interactions index and the density overlap regions indicator. </p> </div> </div> </div>

scholarly journals 1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1390 ◽  
Author(s):  
Ilya G. Shenderovich
Keyword(s):  
Chemical Shift ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Density Functional ◽  
Molecular Structures ◽  
Basis Sets ◽  
Functional Theory ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its 31P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this 31P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported.

Lewis base controlled supramolecular architectures via non-covalent interactions of dioxomolybdenum(vi) complexes with an ONS donor ligand: DFT calculations and biological study

2015 ◽  
Vol 39 (4) ◽  
pp. 2778-2794 ◽  
Author(s):  
Debanjana Biswal ◽  
Nikhil Ranjan Pramanik ◽  
Syamal Chakrabarti ◽  
Nirmalya Chakraborty ◽  
Krishnendu Acharya ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Lewis Base ◽  
Biological Study ◽  
Donor Ligand ◽  
Supramolecular Architectures ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Fascinating supramolecular frameworks of Mo(vi) complexes.

scholarly journals Supramolecular interactions between catalytic species allow rational control over reaction kinetics

2019 ◽  
Vol 10 (39) ◽  
pp. 9115-9124 ◽  
Author(s):  
Abraham J. P. Teunissen ◽  
Tim F. E. Paffen ◽  
Ivo A. W. Filot ◽  
Menno D. Lanting ◽  
Roy J. C. van der Haas ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Reaction Kinetics ◽  
Phase Transfer ◽  
Supramolecular Interactions ◽  
Two Phase ◽  
Phase Transfer Catalysts ◽  
System P ◽  
Non Covalent Interactions ◽  
Rational Control ◽  
Covalent Interactions

The non-covalent interactions between two phase-transfer catalysts allow tuning of reaction kinetics from bimolecular, to pseudo 0th order, to sigmoidal. Kinetic models and DFT calculations are used to obtain detailed insight in the system.

Unveiling the non-covalent interactions of molecular homodimers by dispersion-corrected DFT calculations and collision-induced broadening of ro-vibrational transitions: application to (CH2F2)2 and (SO2)2

2015 ◽  
Vol 17 (8) ◽  
pp. 5659-5669 ◽  
Author(s):  
Nicola Tasinato ◽  
Stefan Grimme
Keyword(s):  
Ir Spectroscopy ◽  
Dft Calculations ◽  
Dissociation Energies ◽  
Non Covalent Interactions ◽  
Vibrational Transitions ◽  
Covalent Interactions

(CH2F2)2 and (SO2)2 are investigated using DFT-D3 computations, and experimental dissociation energies are determined by TDL-IR spectroscopy. DFT-D3 dramatically improves over uncorrected DFT.

Computational insight into the cooperative role of non-covalent interactions in the aza-Henry reaction catalyzed by quinine derivatives: mechanism and enantioselectivity

2016 ◽  
Vol 14 (40) ◽  
pp. 9588-9597 ◽  
Author(s):  
Yunsheng Xue ◽  
Yuhui Wang ◽  
Zhongyan Cao ◽  
Jian Zhou ◽  
Zhao-Xu Chen
Keyword(s):  
Hydrogen Bonding ◽  
Dft Calculations ◽  
Ion Pair ◽  
Henry Reaction ◽  
Brönsted Acid ◽  
Non Covalent Interactions ◽  
Dual Activation ◽  
Covalent Interactions ◽  
Insight Into

DFT calculations reveal the viability of the two possible ion pair-hydrogen bonding and Brønsted acid-hydrogen bonding dual activation modes.

Sign in / Sign up

Export Citation Format

Share Document