Abstract Oligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates form various shape‐persistent geometries, including linear, triangular, rectangular, hexagonal macrocyclic. However, as a result this structural variety, it is oftentimes challenging correlate molecular design with...

We reveal unique hydrogen (H-) bonding patterns and exploit them to control the kinetics, pathways length of supramolecular polymers (SPs). New bisamide-containing monomers were designed elucidate role competing intra- vs. intermolecular H-bonding interactions on kinetics polymerization (SP). Remarkably, two polymerization-inactive metastable states discovered. Contrary previous examples, commonly assumed intramolecularly H-bonded monomer does not evolve into intermolecularly SPs via ring...

Abstract A complex aggregation pathway towards two diastereomeric P and M supramolecular helices arises from the of a short, chiral, rigid oligo(phenyleneethynylene) [OPE, ( S )‐ 1 ]. Thus, while Agg I aggregate is obtained when DCM solution diluted with MCH at room temperature, II generated only after slow heating (353 K)/cooling (273 K) process. Interestingly, during formation (mechanism 1), short chain oligomers are produced, which have great tendency to in plane, yielding brick‐like...

Contrast agents (CAs) are essential in biomedical imaging to aid the diagnosis and therapy monitoring of disease. However, they typically restricted one modality have fixed properties such as size, shape, toxicity profile or photophysical characteristics, which hampers a comprehensive view biological processes. Herein, we introduce rationally designed dye assemblies unique CA platform for simultaneous multimodal multiscale imaging. To this end, synthesized series amphiphilic aza‐BODIPY dyes...

Contrast agents (CAs) are essential in biomedical imaging to aid the diagnosis and therapy monitoring of disease. However, they typically restricted one modality have fixed properties such as size, shape, toxicity profile or photophysical characteristics, which hampers a comprehensive view biological processes. Herein, we introduce rationally designed dye assemblies unique CA platform for simultaneous multimodal multiscale imaging. To this end, synthesized series amphiphilic aza‐BODIPY dyes...

Supramolecular and covalent polymers share multiple structural effects such as chiral amplification, helical inversion, sergeants soldiers, or majority rules, among others. These features are related to the axial structure found in both types of materials, which responsible for their properties. Herein a novel material combining information characteristics from fields polymers, supramolecular (oligo(p-phenyleneethynylene) (OPE)) (poly(acetylene) (PA)), is presented. To achieve this goal,...

A chiral harvesting transmission mechanism is described in poly(acetylene)s bearing oligo(<italic>p</italic>-phenyleneethynylene)s (OPEs) used as rigid achiral spacers and derivatized with pendant groups.

The introduction of a single chiral substituent with switchable conformer equilibrium at the poly(phenyl isocyanate) terminus allowed control helical sense polymer backbone using various external stimuli. Helical enhancement was achieved through domino effect, where assigned by VCD spectroscopy and DFT calculations.

We introduce planarity breaking as a new design strategy for controlled supramolecular polymerization.

An in-depth study of the supramolecular copolymerization behavior N- and C-centered benzene-1,3,5-tricarboxamides (N- C-BTAs) has been conducted in methylcyclohexane solid state. The connectivity amide groups BTAs differs, mixing C-BTAs results copolymers with a blocky microstructure solution. from formation weaker less organized, antiparallel hydrogen bonds between C-BTAs. In methylcyclohexane, helical threefold hydrogen-bonding network present C- N-BTAs is retained mixtures. state,...

We exploit halogen effects to tune metal–metal interactions, nucleation pathways and hetero-seeded growth in supramolecular copolymerizations.

Abstract Oligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates form various shape‐persistent geometries, including linear, triangular, rectangular, hexagonal macrocyclic. However, as a result this structural variety, it is oftentimes challenging correlate molecular design with...

Understanding structure/property correlations in self‐assembly is a key but challenging requirement for developing functional materials. Herein, we explore the importance of ligand geometry to tune photophysical properties (MMLCT vs. MLCT excited states) and pathways metallosupramolecular polymerization. To this end, have designed two hydrophobic Pt(II) complexes, 1 2, containing π‐extended bidentate bipyridine with different substitution pattern, resulting molecular geometries (linear vs...

Supramolecular polymers are often investigated for highly symmetric and planar molecules, such as typically explored BF2 -substituted BODIPY dyes . However, it is surprising that the possibility of desymmetrizing sp3 ...

Chiral allenes self‐assembly following a cooperative mechanism into supramolecular chiral aggregate consisting of two coaxial helices: the internal helix described by allene stack and external which consist in quadruple‐helix four substituents. More precisely, this possesses six axially elements within its structure —the allene, (internal helix) stacks substituents (external 4‐helix)—. Interestingly, slight variations magnitude tilting degree while keeping P‐ or M‐ orientation can vary...

Chiral allenes self‐assembly following a cooperative mechanism into supramolecular chiral aggregate consisting of two coaxial helices: the internal helix described by allene stack and external which consist in quadruple‐helix four substituents. More precisely, this possesses six axially elements within its structure —the allene, (internal helix) stacks substituents (external 4‐helix)—. Interestingly, slight variations magnitude tilting degree while keeping P‐ or M‐ orientation can vary...

Abstract A complex aggregation pathway towards two diastereomeric P and M supramolecular helices arises from the of a short, chiral, rigid oligo(phenyleneethynylene) [OPE, ( S )‐ 1 ]. Thus, while Agg I aggregate is obtained when DCM solution diluted with MCH at room temperature, II generated only after slow heating (353 K)/cooling (273 K) process. Interestingly, during formation (mechanism 1), short chain oligomers are produced, which have great tendency to in plane, yielding brick‐like...

Supramolecular helices that arise from the self-assembly of small organic molecules via non-covalent interactions play an important role in structure and properties corresponding materials. Here we study supramolecular helical aggregation oligo(phenyleneethynylene) monomers a theoretical point view, always guiding studies with experimentally available data. In this way, by systematically increasing number monomer units, optimized n-mer geometries are obtained along absorption circular...

The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways supramolecular polymerization processes, with focus being primarily placed on organic media. Expanding such controlled assemblies in aqueous media by molecular design is, however, still challenging due the difficulty programming noncovalent interactions water. Herein, we tackle this challenge analyzing amphiphilic Pt(II) different...

The design, synthesis and structure elucidation of helical polymers with a predominant sense have been actively studied during the last years due to different applications that these materials can present. polymer be determined by chirality pendants is directly related distance from chiral centre backbone. In order achieve best folding this between polymeric backbone should small, so closer pendant better control. Nevertheless, few examples demonstrated control also possible when spacer...