Soft Materials with Diverse Suprastructures via the Self-Assembly of Metal–Organic Complexes

Titanium-based metal–organic frameworks have been used as an in situ etching template for the self-assembly of graphene oxide to construct NaTi2(PO4)3-rGO composite.

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New Ce(iii) sulfate–tartrate-based MOFs: an insight into the controllable self-assembly of acentric metal–organic complexes

CrystEngComm ◽

10.1039/c3ce41740a ◽

2013 ◽

Vol 15 (48) ◽

pp. 10618 ◽

Cited By ~ 4

Author(s):

Jin-Li Qi ◽

Yue-Qing Zheng ◽

Wei Xu ◽

Hong-Lin Zhu ◽

Jian-Li Lin ◽

...

Keyword(s):

Self Assembly ◽

Organic Complexes ◽

Metal Organic ◽

Insight Into

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Copper-Free One-Pot Sonogashira-Type Coupling for the Efficient Preparation of Symmetric Diarylalkyne Ligands for Metal-Organic Cages

10.26434/chemrxiv.13625783 ◽

2021 ◽

Author(s):

Marc Lehr ◽

Tobias Paschelke ◽

Victoria Bendt ◽

Andre Petersen ◽

Lorenz Pietsch ◽

...

Keyword(s):

Self Assembly ◽

Aryl Halide ◽

Reaction Times ◽

The Self ◽

One Pot ◽

Metal Organic ◽

Type Coupling ◽

Ligand Synthesis

<div> Bipyridine- and benzimidazole-based ligands for the self-assembly of Co4L6 cages were synthesised in short reaction times and high isolated yields directly from aryl halide precursors using a copper-free one-pot Sonogashira-type coupling. This one-pot method circumvents the often time-consuming and challenging ligand synthesis for the preparation and application of cages. </div>

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Porphyrin-based metal coordination polymers with self-assembly pathway-dependent properties for photodynamic and photothermal therapy

10.21203/rs.3.rs-54280/v1 ◽

2020 ◽

Author(s):

Yuyang Miao ◽

Shibo Lv ◽

Daoyuan Zheng ◽

Yuhan Liu ◽

Dapeng Liu ◽

...

Keyword(s):

Coordination Polymers ◽

Self Assembly ◽

Photothermal Therapy ◽

The Self ◽

Metal Coordination ◽

Great Promise ◽

Assembly Process ◽

Assembly Pathway ◽

Metal Organic ◽

Metal Coordination Polymers

Abstract Porphyrin-based metal coordination polymers (MCPs) have attracted numerous attention due to their great promise application in phototherapy including photodynamic therapy (PDT) and photothermal therapy (PTT). However, the detailed self-assembly process of porphyrin-based MCPs still remains poorly understood. This work provides a detailed study of the self-assembly process of MCPs constructed by Mn2+ and TCPP (TCPP: 4,4′,4′′,4′′′-(Porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid)) in aqueous solution. Unlike traditional nucleation and growth mechanism, we discover that there is a metastable metal-organic intermediate which is kinetically favored in the self-assembly process. And the metastable metal-organic intermediate nanotape structures could convert into thermodynamically favored nanosheets through disassembling into monomers followed by reassembling process. Moreover, the two structurally different assemblies exhibit distinct photophysical performances. The intermediate Mn-TCPP aggregates show good light-induced singlet oxygen 1O2 generation for PDT while the thermodynamic favored stable Mn-TCPP aggregates exhibit good photothermal conversion ability as photothermal agents (PTAs). This study could facilitate controlling self-assembly pathway to fabricate complex MCPs with desirable applications.

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Porous Colloidal Hydrogels Formed by Coordination-Driven Self-Assembly of Charged Metal-Organic Polyhedra

10.26434/chemrxiv.13621220.v1 ◽

2021 ◽

Author(s):

Zaoming Wang ◽

Gavin Craig ◽

alexandre legrand ◽

Frederik Haase ◽

Saori Minami ◽

...

Keyword(s):

Self Assembly ◽

Soft Materials ◽

Building Blocks ◽

Internal Cavity ◽

Hydroxyl Groups ◽

Gel Formation ◽

Gas Sorption ◽

Coordination Cages ◽

Metal Organic ◽

Supramolecular Polymerization

Introduction of porosity into supramolecular gels endows soft materials with functionalities for molecular encapsulation, release, separation and conversion. Metal-organic polyhedra (MOPs), discrete coordination cages containing an internal cavity, have recently been employed as building blocks to construct polymeric gel networks with potential porosity. However, most of the materials can only be synthesized in organic solvents, and the examples of porous, MOP-based hydrogels are scarce. Here, we demonstrate the fabrication of porous hydrogels based on [Rh2(OH-bdc)2]12, a rhodium-based MOP containing hydroxyl groups on its periphery (OH-bdc = 5-hydroxy-1,3-benzenedicarboxylate). By simply deprotonating [Rh2(OH-bdc)2]12 with the base NaOH, the supramolecular polymerization between MOPs and organic linkers can be induced in the aqueous solution, leading to the kinetically controllable formation of hydrogels with hierarchical colloidal networks. When heating the deprotonated MOP, Nax[Rh24(O-bdc)x(OH-bdc)24-x], to induce gelation, the MOP was found to partially decompose, affecting the mechanical property of the resulting gels. By applying a post-synthetic deprotonation strategy, we show that the deprotonation degree of the MOP can be altered after the gel formation without serious decomposition of the MOPs. Gas sorption measurements confirmed the permanent porosity of the corresponding aerogels obtained from these MOP-based hydrogels, showing potentials for applications in gas sorption and catalysis.

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Solvent-dependent supramolecular self-assembly of boron cage pillared metal–organic frameworks for selective gas separation

CrystEngComm ◽

10.1039/d0ce00142b ◽

2020 ◽

Vol 22 (15) ◽

pp. 2649-2655 ◽

Cited By ~ 3

Author(s):

Yuanbin Zhang ◽

Lingyao Wang ◽

Jianbo Hu ◽

Simon Duttwyler ◽

Xili Cui ◽

...

Keyword(s):

Gas Separation ◽

Self Assembly ◽

Metal Organic Frameworks ◽

The Self ◽

Metal Organic ◽

Assembly Behavior

A family of microporous boron cage pillared supramolecular metal–organic frameworks are synthesized with the self-assembly behavior controlled by solvents. Interpenetrated BSF-4 is potential for highly selective C2H2/C2H4 and C2H2/CO2 separation.

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Spatiotemporal Control of Supramolecular Polymerization and Gelation of Metal-Organic Polyhedra

10.26434/chemrxiv.13414646.v1 ◽

2020 ◽

Author(s):

alexandre legrand ◽

Li-Hao Liu ◽

Philipp Royla ◽

Takuma Aoyama ◽

Gavin Craig ◽

...

Keyword(s):

Acid Concentration ◽

Self Assembly ◽

Colloidal Particles ◽

Soft Materials ◽

Supramolecular Materials ◽

Time Resolved ◽

Colloidal Gel ◽

Metal Organic ◽

Spatiotemporal Control ◽

Gel Network

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA), and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption and 1H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

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