Truncated trigonal prismatic tubular crystals consisting of a zeolite L-mimic metal–organic framework

Noh, Tae Hwan; Jang, Jaeseong; Hong, W.; Lee, Haeri; Jung, Ok‐Sang

doi:10.1039/c4cc03097d

Cited by 18 publications

(32 citation statements)

References 39 publications

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“…The fabrication of these hierarchically organized photoactive materials and their use as artificial antenna systems, pioneered by the Calzaferri group,,,,,, has been thoroughly investigated and the acquired knowledge played a seminal role, for example, in extending their scope to biomedical uses . Also importantly, dye‐zeolite L hybrids stimulated the quest of new host matrices for luminescent supramolecular systems: not only zeolite frameworks of diverse shape and composition,, but also mesoporous silicas/organosilicas,,,, 1D macrocycle channels,, and MOFs ,,…”

Section: Organization Of Complex Species In 1dmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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Empty spaces are abhorred by nature, which immediately rushes in to fill the void. Humans have learnt pretty well how to make ordered empty nanocontainers, and to get useful products out of them. When such an order is imparted to molecules, new properties may appear, often yielding advanced applications. This review illustrates how the organized void space inherently present in various materials: zeolites, clathrates, mesoporous silica/organosilica, and metal organic frameworks (MOF), for example, can be exploited to create confined, organized, and self-assembled supramolecular structures of low dimensionality. Features of the confining matrices relevant to organization are presented with special focus on molecular-level aspects. Selected examples of confined supramolecular assemblies - from small molecules to quantum dots or luminescent species - are aimed to show the complexity and potential of this approach. Natural confinement (minerals) and hyperconfinement (high pressure) provide further opportunities to understand and master the atomistic-level interactions governing supramolecular organization under nanospace restrictions.

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Section: Organization Of Complex Species In 1dmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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“…17 To the best of our knowledge, only a zeolite L-mimic metal-organic framework (ZLMOF) has achieved a tubular shape just recently, 18 and no report on tuning MOP-18, or other MOP crystals to such a special morphology is available.…”

Section: Introductionmentioning

confidence: 99%

Ammonia assisted formation of tubular MOP-18 crystals

2014

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Tubular MOP-18 crystals have been successfully prepared by cooling-induced crystallization from copper hydroxide nanostrands and 5-dodecyloxybenzene-1,3-dicarboxylic acid DMF (N, N-dimethyl-formamide)/ammonia solution. The dependence of the crystal morphologies on the cooling rate is investigated in detail. Slower cooling rate results in larger and longer MOP-18 tubes. Ammonia in DMF solution plays a crucial role in the formation of MOP-18 tubes. It deprotonates the acid ligand to trigger the nucleation of MOP-18 and leads the growth of tubular crystals. A "diffusion driven instability" growth mechanism is proposed. The outside surfaces of crystals are able to get better material supply from the surrounding solution and keep continuous growth. While the inner cavity part not only get worse material supply but also dissolve the inner walls to balance the local saturated solubility of MOP-18 in DMF at certain temperature, and results the formation of tubes.

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“…MOFs having onedimensional (1D) channel systems are particularly appealing for the fabrication of host-guest multifunctional hybrid materials 71 114 . A nice example is the "zeolite L-mimic metal-organic framework (ZLMOF)" built by Noh et al from [Ag 4 Ni(L) 3 ]•3.5H 2 O ((L 2− = bis(methylthio)methylenepropanedioate), which features so-called "caterpillar-shape nanochannels" 115 . This ZLMOF represents to date the best structural mimic of zeolite L (ZL), as its channels have comparable shape and size.…”

Section: Introductionmentioning

confidence: 99%

“…The free diameter of zeolite L channels (corresponding to the size of the channel opening) is 7.2 Å, while the free diameter of the ZLMOF channels is limited to 7.55 Å by the ligands' thiomethyl groups 115 . Both zeolite L and ZLMOF feature hexagonal arrays of channels, running along the c-axis; moreover, for both as-prepared materials, the channels contain clusters of water molecules 115,116 .…”

Section: Introductionmentioning

confidence: 99%

The Different Organization of Water in Zeolite L and Its MOF Mimic

Tabacchi¹,

Fois²

2019

Preprint

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Abstract:<div>Confinement of molecules inside one dimensional arrays of channel-shaped cavities has led to an impressive number of technologically interesting materials. However, the interactions governing the properties of the supramolecular aggregates still remain obscure, even in the case of the most common guest molecule: water. Herein, we use computational chemistry methods (#compchem) to study the water organization inside two different channel-type environments: zeolite L – a widely used matrix for inclusion of dye molecules, and ZLMOF – the closest metal-organic-framework mimic of zeolite L. In ZLMOF, the methyl groups of the ligands protrude inside the channels, creating nearly isolated nanocavities. These cavities host well-separated ring-shaped clusters of water molecules, dominated mainly by water-water hydrogen bonds. ZLMOF channels thus provide arrays of „isolated supramolecule“ environments, which might be exploited for the individual confinement of small species with interesting optical or catalytic properties. In contrast, the one dimensional nanochannels of zeolite L contain a continuous supramolecular structure, governed by the water interactions with potassium cations and by water-water hydrogen bonds. Water molecules impart a significant energetic stabilization to both materials, which increases by increasing the water content in ZLMOF, while the opposite trend is observed in zeolite L. The water network in zeolite L contains an intriguing hyper-coordinated structure, where a water molecule is surrounded by 5 strong hydrogen bonds. Such a structure, here described for the first time in zeolites, can be considered as a water pre-dissociation complex and might explain the experimentally detected high proton activity in zeolite L nanochannels. </div>

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Truncated trigonal prismatic tubular crystals consisting of a zeolite L-mimic metal–organic framework

Abstract: Research on the construction, crystal morphology, and functions of a novel zeolite L-mimic metal-organic framework (ZLMOF) was carried out. Treatment of the tubular crystals with AgBF4 in acetone at 40 °C smoothly coated the surface of the ZLMOF crystals with silver(0) nanoparticles.

Cited by 18 publications

References 39 publications

Supramolecular Organization in Confined Nanospaces

Supramolecular Organization in Confined Nanospaces

Ammonia assisted formation of tubular MOP-18 crystals

The Different Organization of Water in Zeolite L and Its MOF Mimic

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