In-MOFs based on amide functionalised flexible linkers

2017 ◽  
Vol 201 ◽  
pp. 327-335 ◽  
Author(s):  
J. Haddad ◽  
G. F. S. Whitehead ◽  
A. P. Katsoulidis ◽  
M. J. Rosseinsky
Keyword(s):  
Hydrogen Bonding ◽  
Functional Group ◽  
Close Packing ◽  
Supramolecular Interactions ◽  
Indium Hydroxide ◽  
Group Orientation ◽  
Accessible Volume ◽  
Succinamic Acid ◽  
Cylindrical Pores ◽  
Metal Organic

Two new amide functionalised metal–organic frameworks, In(OH)CSA and In(OH)PDG, were synthesized using two flexible linkers, N-(4-carboxyphenyl)succinamic acid (CSA) and N,N′-(1,4-phenylenedicarbonyl)diglycine (PDG), respectively. Both structures consist of corner-sharing {InO4(OH)2} octahedra in the form of trans indium hydroxide chains, which are interconnected by the dicarboxylate linkers to form stacked 2-dimensional layers. The different symmetries and configurations of the flexible and rigid features on the linkers results in different supramolecular interactions dominating between linkers, resulting in different shaped pores and functional group orientation. In(OH)CSA lacks hydrogen bonding between linkers, which results in close packing between the layers and very small solvent accessible pores running perpendicular to the plane of the layers. In(OH)PDG exhibits strong intra- and interlayer hydrogen bonding, which prevents the layers from close packing and results in larger cylindrical pores running parallel to the indium hydroxide chains, producing a total accessible volume of 25% of the unit cell volume.

scholarly journals Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 697 ◽  
Author(s):  
Mohammad S. Yazdanparast ◽  
Victor W. Day ◽  
Tendai Gadzikwa
Keyword(s):  
Hydrogen Bonding ◽  
Pore Volume ◽  
Reliable Method ◽  
Metal Organic Framework ◽  
Low Density ◽  
Paddle Wheel ◽  
Accessible Volume ◽  
New Material ◽  
Metal Organic ◽  
Organic Framework

Pillared paddle-wheel-based metal-organic framework (MOF) materials are an attractive target as they offer a reliable method for constructing well-defined, multifunctional materials. A drawback of these materials, which has limited their application, is their tendency to form catenated frameworks with little accessible volume. To eliminate this disadvantage, it is necessary to investigate strategies for constructing non-catenated pillared paddle-wheel MOFs. Hydrogen-bonding substituents on linkers have been postulated to prevent catenation in certain frameworks and, in this work, we present a new MOF to further bolster this theory. Using 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylic acid, BPDC-(NH2)2, linkers and dipyridyl glycol, DPG, pillars, we assembled a MOF with pcu topology. The new material is non-catenated, exhibiting large accessible pores and low density. To the best of our knowledge, this material constitutes the pcu framework with the largest pore volume and lowest density. We attribute the lack of catenation to the presence of H-bonding substituents on both linkers.

scholarly journals Exploring the Halogen-Bonded Cocrystallization Potential of a Metal-Organic Unit Derived from Copper(ii) Chloride and 4-Aminoacetophenone

Materials ◽  
2020 ◽  
Vol 13 (10) ◽  
pp. 2385
Author(s):  
Vinko Nemec ◽  
Katarina Lisac ◽  
Marin Liović ◽  
Ivana Brekalo ◽  
Dominik Cinčić
Keyword(s):  
Hydrogen Bonding ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Supramolecular Interactions ◽  
X Ray Diffraction ◽  
Square Planar ◽  
Metal Organic ◽  
Acetyl Group ◽  
Conventional Solution

In this work, we describe a novel halogen-bonded metal-organic cocrystal involving a square-planar Cu(ii) complex and 1,4-diiodotetrafluorobenzene (14tfib) by utilizing an amine ligand whose pendant acetyl group enables halogen bonding. The cocrystal was prepared by both mechanochemical synthesis (liquid-assisted grinding) and the conventional solution-based method. Crystal structure determination by single crystal X-ray diffraction revealed that the dominant supramolecular interactions are the I···O halogen bond between 14tfib and CuCl2(aap)2 building blocks, and the N–H···Cl hydrogen bonds between CuCl2(aap)2 molecules. The combination of halogen and hydrogen bonding leads to the formation of a 2D network. Overall, this work showcases an example of the possibility for extending the complexity of metal-organic crystal structures by using halogen bonding in a way that does not affect other hydrogen bonding synthons.

scholarly journals One-dimensional ladder gallium coordination polymer

2019 ◽  
Vol 75 (11) ◽  
pp. 1607-1612
Author(s):  
Andrea B. Simões ◽  
Flávio Figueira ◽  
Ricardo F. Mendes ◽  
Jéssica S. Barbosa ◽  
João Rocha ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Coordination Polymer ◽  
Dicarboxylic Acid ◽  
Experimental Methods ◽  
Close Packing ◽  
Supramolecular Interactions ◽  
One Pot ◽  
One Dimensional ◽  
Microwave Assisted ◽  
Hydrogen Bonding Interactions

A one-dimensional ladder-type coordination polymer, poly[[(μ2-hydroxido)(μ2-1H-pyrazole-3,5-dicarboxylato)gallium(III)] monohydrate], [Ga(C5H2N2O4)(OH)(H2O)] n or [Ga(HPDC)(OH)(H2O)] n , I, isotypic with a V3+ coordination polymer previously reported by Chen et al. [J. Coord. Chem. (2008). 61, 3556–3567] was prepared from Ga3+ and pyrazole-3,5-dicarboxylic acid monohydrate (H3PDC·H2O). Compound I was isolated using three distinct experimental methods: hydrothermal (HT), microwave-assisted (MWAS) and one-pot (OP) and the crystallite size should be fine-tuned according to the method employed. The coordination polymeric structure is based on a dimeric Ga3+ moiety comprising two μ2-bridging hydroxide groups, which are interconnected by HPDC2− anionic organic linkers. The close packing of individual polymers is strongly directed by the supramolecular interactions, namely several O—H...O and N—H...O hydrogen-bonding interactions.

N-Functionality Actuated Largely Improved CO2 Adsorption and Nanomolar Turn-on Detection of Organo-Toxins with Guest-Induced Fluorescence Modulation in Isostructural Diamondoid Frameworks

2021 ◽  
Author(s):  
Manpreet Singh ◽  
Athulya S. Palakkal ◽  
Renjith S. Pillai ◽  
Subhadip Neogi
Keyword(s):  
Carbon Dioxide ◽  
Functional Group ◽  
Co2 Adsorption ◽  
Metal Organic Frameworks ◽  
Turn On ◽  
Metal Organic ◽  
Fluorescence Modulation

Metal-organic frameworks (MOFs) have surfaced as incipient class of multifaceted materials for selective carbon dioxide (CO2) adsorption and luminescent detection of assorted classes of lethal organo-aromatics, where functional group assisted...

scholarly journals Theoretical hydrogen bonding calculations and proton conduction for Eu(iii)-based metal–organic framework

RSC Advances ◽  
2021 ◽  
Vol 11 (19) ◽  
pp. 11495-11499
Author(s):  
Lu Feng ◽  
Tian-Yu Zeng ◽  
Hao-Bo Hou ◽  
Hong Zhou ◽  
Jian Tian
Keyword(s):  
Hydrogen Bonding ◽  
Theoretical Calculation ◽  
Proton Transport ◽  
Metal Organic Framework ◽  
Proton Conduction ◽  
Transport Channel ◽  
Proton Conducting ◽  
Metal Organic ◽  
Organic Framework

A water-mediated proton-conducting Eu(iii)-MOF has been synthesized, which provides a stable proton transport channel that was confirmed by theoretical calculation.

Preferential adsorption of ethane over ethylene on a Zr-based metal-organic framework: impacts of C-H···N hydrogen bonding

2021 ◽  
Author(s):  
Yaping Zhang ◽  
Daofei Lv ◽  
Jiayu Chen ◽  
Zewei Liu ◽  
Chongxiong Duan ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Surface Area ◽  
Energy Efficient ◽  
Metal Organic Framework ◽  
Bet Surface Area ◽  
Preferential Adsorption ◽  
Metal Organic ◽  
Organic Framework

The separation of ethylene/ethane mixture using energy-efficient technologies is important but challenging. Here, we prepared a Zr-based metal-organic framework (MOF-545) possessing high Brunauer-Emmett-Teller (BET) surface area of 2265.4 m2/g, and...

Interplay of coordinative and supramolecular interactions in formation of a series of metal–organic complexes bearing diverse dimensionalities

2009 ◽  
pp. 5365 ◽  
Author(s):  
Jian-Qiang Liu ◽  
Ya-Nan Zhang ◽  
Yao-Yu Wang ◽  
Jun-Cheng Jin ◽  
Elmira Kh. Lermontova ◽  
...  
Keyword(s):  
Supramolecular Interactions ◽  
Organic Complexes ◽  
Metal Organic

A New Organic-Inorganic Hybrid Based on L-Arginine and Polyoxoanion

2015 ◽  
Vol 1105 ◽  
pp. 335-338
Author(s):  
Qiong Wu ◽  
Jing Lu ◽  
Xiao Lin Ji ◽  
Tao Yu Zou ◽  
Zhen Fang Qiao ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Sodium Cation ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Inorganic Hybrid ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Photocatalytic Activities ◽  
Metal Organic ◽  
Supramolecular Networks

Modifying polyoxometalates with organic and/or metal-organic moieties is a widely adopted method for broading the range of properties. In this work a new polyoxometalate constructed from Anderson-type polyoxoanions and L-arginine (Arg =L-arginine) molecules Na [CrMo6(OH)6O18]}(H2Arg)2·8H2O(1) has been synthesized via conventional method and characterized by routine techniques. Single-crystal X-Ray diffraction analysis shows that compound 1 is constructed by chiralL-arginine grafted Anderson-type clusters, sodium cation and water molecules which are further stabilized by hydrogen bonding interactions constitute 3D supramolecular networks. In addition, both antitumor behavior and photocatalytic activities of compound 1 were investigated.

Supramolecular Interactions in Aromatic Structures for Non-Optical and Optical Chemosensors of Explosive Chemicals

2021 ◽  
Vol 317 ◽  
pp. 202-207
Author(s):  
Juan Matmin ◽  
Nur Fatiha Ghazalli ◽  
Fazira Ilyana Abdul Razak ◽  
Hendrik O. Lintang ◽  
Mohamad Azani Jalani
Keyword(s):  
Hydrogen Bonding ◽  
High Performance ◽  
Molecular Design ◽  
Optical Sensing ◽  
Green Emission ◽  
Supramolecular Interactions ◽  
Side Chain ◽  
Optical Chemosensors ◽  
Random Aggregate ◽  
Metal Metal

The scientific investigation based on the molecular design of aromatic compounds for high-performance chemosensor is challenging. This is because their multiplex interactions at the molecular level should be precisely determined before the desired compounds can be successfully used as sensing materials. Herein, we report on the molecular design of chemosensors based on aromatic structures of benzene as the organic motif of benzene-1,3,5-tricarboxamides (BTA), as well as the benzene pyrazole complexes (BPz) side chain, respectively. In the case of BTA, the aromatic benzene acts as the centre to allow the formation of π–π stacking for one-dimensional materials having rod-like arrangements that are stabilized by threefold hydrogen bonding. We found that when nitrate was applied, the rod-like BTA spontaneously formed into a random aggregate due to the deformation of its hydrogen bonding to form inactive nitroso groups for non-optical sensing capability. For the optical chemosensor, the aromatic benzene is decorated as a side-chain of BPz to ensure that cage-shaped molecules make maximum use of their centre providing metal-metal interactions for fluorescence-based sensing materials. In particular, when exposed to benzene, Cu-BPz displayed a blue-shift of its original emission band from 616 to 572 nm (Δ = 44 nm) and emitted bright orange to green emission colours. We also observe a different mode of fluorescence-based sensing materials for Au-BPz, which shows a particular quenching mechanism resulting in 81% loss of its original intensity on benzene exposure to give less red-orange emission (λ = 612 nm). The BTA and BPz synthesized are promising high-performance supramolecular chemosensors based on the non-optical and optical sensing capability of a particular interest analyte.

Competition between coordination bonds and hydrogen bonding interactions in solvatomorphs of copper(II), cadmium(II) and cobalt(II) complexes with 2,2′-bipyridyl and acetate

2019 ◽  
Vol 234 (2) ◽  
pp. 119-128 ◽  
Author(s):  
José Antônio do Nascimento Neto ◽  
Cameron Capeletti da Silva ◽  
Leandro Ribeiro ◽  
Ana Karoline Silva Mendanha Valdo ◽  
Felipe Terra Martins
Keyword(s):  
Hydrogen Bonding ◽  
Dft Calculations ◽  
Organic Molecules ◽  
Energy Difference ◽  
Water Molecules ◽  
Coordination Numbers ◽  
Lattice Water ◽  
Hydrogen Bonding Interactions ◽  
Metal Organic ◽  
Coordination Bonds

Abstract The delicate balance among conformation, coordination bonds and hydrogen bonding has been probed in solvatomorphs of known metal-organic molecules synthesised from copper(II), cadmium(II) and cobalt(II) with acetate (OAc) and 2,2′-bipyridine (bipy). The Cu(OAc)2(bipy) complex, isolated as a pentahydrate, has the acetate ligands oriented to opposite sides of the coordination square plane. DFT calculations show the energy difference between this structure and a syn form amount to approximately 16 kJ/mol. The presence of lattice water enables the formation of O–H···O hydrogen bonds with the acetate ligands. Different coordination numbers and energies are found as a function of the number of water molecules co-crystallising in the Cd(OAc)2(bipy)(OH2)·3H2O and [Co(OAc)(bipy)2](OAc)·3H2O complexes.

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