Xanthene[n]arenes: Exceptionally Large, Bowl-shaped Macrocyclic Building Blocks Suitable for Self-Assembly

<div>A new class of macrocycles denoted as “xanthene[n]arenes” was synthesized. In contrast to most other macrocycles, they feature a rigid bowl-shape, required for the synthesis of cavitands and for the self-assembly to molecular capsules via non-covalent interactions. The derivatization potential of the novel macrocycles was demonstrated on the xanthene[3]arene scaffold. Beside a deep cavitand, a modified macrocycle was synthesized that self-assembles into a hydrogen-bonded tetrameric capsule. Both supramolecular systems display host-guest binding properties, demonstrating the potential of xanthene[n]arenes as a new set of macrocyclic building blocks.</div>

Self-assembly of water-soluble silver nanoclusters: superstructure formation and morphological evolution

Nanoscale ◽

10.1039/c7nr06359h ◽

2017 ◽

Vol 9 (48) ◽

pp. 19191-19200 ◽

Cited By ~ 27

Author(s):

Jinglin Shen ◽

Zhi Wang ◽

Di Sun ◽

Guokui Liu ◽

Shiling Yuan ◽

...

Keyword(s):

Self Assembly ◽

Morphological Evolution ◽

Functional Materials ◽

Building Blocks ◽

Water Soluble ◽

Silver Nanoclusters ◽

Efficient Approach ◽

Supramolecular self-assembly, based on non-covalent interactions, has been employed as an efficient approach to obtain various functional materials from nanometer-sized building blocks, in particular, [Ag6(mna)6]6−, mna = mercaptonicotinate (Ag6-NC).

Reorganization of Self-Assembled DNA-Based Polymers Using Orthogonally Addressable Building Blocks

10.26434/chemrxiv.13643702.v1 ◽

2021 ◽

Author(s):

Serena Gentile ◽

Erica Del Grosso ◽

Leonard J. Prins ◽

Francesco Ricci

Keyword(s):

Self Assembly ◽

Rational Design ◽

Building Blocks ◽

Binding Domain ◽

Sticky Ends ◽

Self Assembled ◽

Block Structures ◽

Taking advantage of the addressability and programmability of DNA/DNA non-covalent interactions we report here the rational design of orthogonal DNA-based addressable tiles that self-assemble into polymer-like structures that can be reconfigured and reorganized by external inputs. The different tiles share the same 5-nucleotide sticky ends responsible for self-assembly but are rationally designed to contain a specific regulator-binding domain that can be orthogonally targeted by different DNA regulator strands (activators and inhibitors). We show that by sequentially adding specific activators and inhibitors it is possible to re-organize in a dynamic and reversible way the formed polymer-like structures to display well-defined distributions: homopolymers made of a single tile, random polymers in which different tiles are distributed randomly and block structures in which the tiles are organized in segments.

Supramolecular organization of phthalocyanines: from solution to surface

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424609000747 ◽

2009 ◽

Vol 13 (04n05) ◽

pp. 471-480 ◽

Cited By ~ 9

Author(s):

M. Victoria Martínez-Díaz ◽

Giovanni Bottari

Keyword(s):

Photophysical Properties ◽

Building Blocks ◽

Supramolecular Interactions ◽

Supramolecular Organization ◽

Supramolecular Systems ◽

Ligand Interactions ◽

Donor Acceptor ◽

Interesting Class ◽

Phthalocyanines are an interesting class of aromatic macrocycles which possess exciting electrical, redox and photophysical properties that make them ideal building blocks for applications in different technological fields. However, the incorporation of phthalocyanines into devices is often tied to the possibility of organizing these macrocycles into arrays using supramolecular interactions. To date, several supramolecular motifs such as hydrogen-bonding, donor-acceptor or metal-ligand interactions have been used to promote the phthalocyanines' organization in solution. Furthermore, such weak, non-covalent interactions have also been widely employed to foster the organization of these macrocycles in condensed phases such as liquid-crystals or thin films. This micro-review provides a brief overview of the contribution made by some research groups in Spain towards the preparation of organized phthalocyanine-based supramolecular systems.

Design of catalytic metal-organic assemblies via shape complementarity and conformational constraints in dual curvature ligands

10.26434/chemrxiv-2021-4z45w ◽

2021 ◽

Author(s):

Cui-Lian Liu ◽

Eduard Bobylev ◽

Brice Kauffmann ◽

Koen Robeyns ◽

Yann Garcia ◽

...

Keyword(s):

Self Assembly ◽

Building Blocks ◽

Alder Reaction ◽

The Self ◽

Supramolecular Catalysis ◽

Shape Complementarity ◽

Large Structures ◽

Metal Organic ◽

Non-covalent interactions play an essential role in the folding and self-assembly of large biological assemblies. These interactions are not only a driving force for the formation of large structures but also control conformation and com-plementary shapes of subcomponents that promote the diversity of structures and functions of the resulting assemblies. Understanding how non-covalent interactions direct self-assembly and the effect of conformation and complementary shapes on self-assembled structures will help design artificial supramolecular systems with extended components and functions. Herein, we develop a strategy for controlling more complex self-assembly with lower symmetry and flexible building blocks that combine endohedral non-covalent interactions with a dual curvature in the ligand backbone to give additional shape complementarity. A Diels-Alder reaction was used to break the symmetry of the diazaanthracene units of the ligands to give dual curvature ligands with different shapes and endohedral groups (L1-L3). The self-assembly studies of these ligands demonstrated that non-covalent interactions and shape complementary effectively control the self-assembly and enable the design of cages for supramolecular catalysis.

Reactive Template-Induced Self-Assembly to Ordered Mesoporous Polymer and Carbon

MRS Proceedings ◽

10.1557/opl.2013.958 ◽

2013 ◽

Vol 1549 ◽

pp. 143-147

Author(s):

Yeru Liang ◽

Ruowen Fu ◽

Dingcai Wu

Keyword(s):

Self Assembly ◽

Covalent Bond ◽

Building Blocks ◽

Mesoporous Polymer ◽

Organic Templates ◽

Ordered Mesoporous ◽

Synthetic Procedure ◽

Covalent Interactions ◽

End Group

ABSTRACTAs an important method for preparing ordered mesoporous polymer and carbon, organic template directed self-assembly is facing challenges because of the weak non-covalent interactions between the organic templates and the building blocks. Herein we developed a novel synthetic procedure based on a reactive template-induced self-assembly to construct ordered mesoporous framework. The aldehyde end-group of reactive template can react with the building blocks (i.e., resol) to form a stable covalent bond during the self-assembly process. This leads to an enhanced interaction between resol and template and thus achieves the formation of ordered mesostructure.

Reorganization of Self-Assembled DNA-Based Polymers Using Orthogonally Addressable Building Blocks

10.26434/chemrxiv.13643702 ◽

2021 ◽

Author(s):

Serena Gentile ◽

Erica Del Grosso ◽

Leonard J. Prins ◽

Francesco Ricci

Keyword(s):

Self Assembly ◽

Rational Design ◽

Building Blocks ◽

Binding Domain ◽

Sticky Ends ◽

Self Assembled ◽

Block Structures ◽

Taking advantage of the addressability and programmability of DNA/DNA non-covalent interactions we report here the rational design of orthogonal DNA-based addressable tiles that self-assemble into polymer-like structures that can be reconfigured and reorganized by external inputs. The different tiles share the same 5-nucleotide sticky ends responsible for self-assembly but are rationally designed to contain a specific regulator-binding domain that can be orthogonally targeted by different DNA regulator strands (activators and inhibitors). We show that by sequentially adding specific activators and inhibitors it is possible to re-organize in a dynamic and reversible way the formed polymer-like structures to display well-defined distributions: homopolymers made of a single tile, random polymers in which different tiles are distributed randomly and block structures in which the tiles are organized in segments.

Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions

Chemical Society Reviews ◽

10.1039/c4cs00497c ◽

2015 ◽

Vol 44 (8) ◽

pp. 2543-2572 ◽

Cited By ~ 235

Author(s):

Christina Rest ◽

Ramesh Kandanelli ◽

Gustavo Fernández

Keyword(s):

Self Assembly ◽

Supramolecular Polymers ◽

Supramolecular Systems ◽

Multiple Systems ◽

Cooperative Phenomena ◽

Self Assembled ◽

High Degree ◽

Covalent Interactions ◽

Degree Of Order

Cooperative phenomena exhibit the basis for the hierarchical self-assembly of multiple systems in nature. Motivated by the high degree of order in these structures, a large number of supramolecular polymers have been designed whose aggregation follows a cooperative pathway. Herein, we have classified the supramolecular systems depending on the cooperative non-covalent forces driving their formation.

A Bottom-Up Approach to Solution-Processed, Atomically Precise Graphitic Cylinders on Surfaces

10.26434/chemrxiv.7158959 ◽

2018 ◽

Author(s):

Erik Leonhardt ◽

Jeff M. Van Raden ◽

David Miller ◽

Lev N. Zakharov ◽

Benjamin Aleman ◽

...

Keyword(s):

Self Assembly ◽

Carbon Nanostructures ◽

Carbon Nanomaterials ◽

Circle Packing ◽

Pyrolytic Graphite ◽

Building Blocks ◽

Bottom Up ◽

Casting Technique ◽

New Class ◽

Solution Casting Technique

Extended carbon nanostructures, such as carbon nanotubes (CNTs), exhibit remarkable properties but are difficult to synthesize uniformly. Herein, we present a new class of carbon nanomaterials constructed via the bottom-up self-assembly of cylindrical, atomically-precise small molecules. Guided by supramolecular design principles and circle packing theory, we have designed and synthesized a fluorinated nanohoop that, in the solid-state, self-assembles into nanotube-like arrays with channel diameters of precisely 1.63 nm. A mild solution-casting technique is then used to construct vertical “forests” of these arrays on a highly-ordered pyrolytic graphite (HOPG) surface through epitaxial growth. Furthermore, we show that a basic property of nanohoops, fluorescence, is readily transferred to the bulk phase, implying that the properties of these materials can be directly altered via precise functionalization of their nanohoop building blocks. The strategy presented is expected to have broader applications in the development of new graphitic nanomaterials with π-rich cavities reminiscent of CNTs.