Exploiting halido ligands to control nucleation pathways and Pt⋯Pt interactions in supramolecular co-polymerizations

Matern, Jonas; Fernández, Zulema; Fernández, Gustavo

doi:10.1039/d2cc04626a

Cited by 9 publications

(3 citation statements)

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“…The results show that the T e of 1 and 2 at 25 μM are 311.9 and 300.1 K, respectively, lower than 319.0 K for [ 1 ] : [ 2 ]=1 : 1 ([ 1 ]+[ 2 ]=50 μM, Figure 5c and Tables S8 and S9), which rule out self‐sorting assembly in the mixed components. Unlike the self‐sorting supramolecular polymerization demonstrated in the literature, the above results show that the nucleation process of this system is heterogeneous nucleation [4, 17, 25] . This may be due to the similar homo‐ and hetero‐free energy of interaction between 1 and 2 , suggesting that the co‐assembly of 1 and 2 is random for both nucleation and elongation processes.…”

Section: Resultsmentioning

confidence: 42%

“…Unlike the self-sorting supramolecular polymerization demonstrated in the literature, the above results show that the nucleation process of this system is heterogeneous nucleation. [4,17,25] This may be due to the similar homo-and hetero-free energy of interaction between 1 and 2, suggesting that the co-assembly of 1 and 2 is random for both nucleation and elongation processes.…”

Section: Resultsmentioning

confidence: 97%

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Supramolecular Copolymers Under Kinetic, Thermodynamic, or Pathway‐Switching Control

et al. 2023

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Supramolecular copolymers have attracted much attention due to their potential functionalities. However, the co-assembly strategies to construct coassemblies of small molecules with well-defined sequence structures are still limited, especially for more complex crystalline block co-assemblies. Herein, we target this challenge by designing Ir III complexes 1 and 2, which possess unique self-assembly pathways and are capable of forming crystalline assemblies in aqueous systems. Specifically, block and random co-assemblies of 1 and 2 can be synthesized by kinetic and thermodynamic control, respectively. Meanwhile, by adjusting the water content to orthogonalize the on-pathway and the off-pathway, an unprecedented pathway-switching approach is realized to synthesize block and random coassemblies. By coupling the kinetic pathways, the present co-assembly strategies are expected to pave the way for the synthesis of crystalline co-assemblies of small molecules and the construction of organic heterostructures.

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Section: Resultsmentioning

confidence: 42%

Section: Resultsmentioning

confidence: 97%

Supramolecular Copolymers Under Kinetic, Thermodynamic, or Pathway‐Switching Control

et al. 2023

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“…The incorporation of metal ions not only enriches the systems with unique redox, optical, electronic, and magnetic properties, but also provides additional intermolecular interaction sites (i.e. metal–metal interactions, M–X···H interactions) that give access to complex energy landscapes. − In this context, d 8 transition metal complexes (mostly Pt(II) and Pd(II)) of mono- and polydentate N-heterocyclic aromatic ligands are especially important, as their square planar geometry allows directional π–π stacking of the aromatic scaffolds, facilitating the formation of one-dimensional (1D) nanostructures. − This in turn provides favorable circumstances to enforce short metal–metal contacts that enable new electronic transitions, such as low energy metal–metal-to-ligand charge transfer (MMLCT) states. − These complex intermolecular interactions give rise to unique photoluminescence properties in supramolecular assemblies, providing important applications in optoelectronic, sensing, and bioimaging. − To date, investigations on structure–property relationships to stabilize the MMLCT state in supramolecular polymers have revealed the importance of ligand design (i.e. mono/polydentate, inclusion of additional noncovalent forces such as H-bonding) and coordination geometry (i.e.…”

Section: Introductionmentioning

confidence: 99%

Controlling Molecular Packing in Aqueous Metallosupramolecular Self-assembly by Ligand Geometry

Sutar

Dünnebacke

Fernández

et al. 2023

Precision Chemistry

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The coordination geometry of d 8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes, with a focus being primarily placed on organic media. Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is, however, still challenging due to the difficulty in programming noncovalent interactions in water. Herein, we tackle this challenge by analyzing the aqueous selfassembly of amphiphilic Pt(II) complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media. To this end, we have designed two Pt(II) complexes, 1 and 2, containing an identical oligophenyleneethynylene (OPE)-based aromatic scaffold that differ in the molecular geometry (linear vs V-shaped) imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media. Even though both molecules follow the isodesmic mechanism of self-assembly, their structural difference strongly influences the molecular packing in aqueous media, which in turn impacts the photophysical properties (i.e. absence or presence of MMLCT) and the self-assembly outcome. While the molecular geometry for 2 enforces short Pt•••Pt contacts driven by an efficient face-to-face stacking of the OPE backbone, the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt•••Pt contacts. Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.

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Three‐Component Multiblock 1D Supramolecular Copolymers of Ir(III) Complexes with Controllable Sequences

Chen,

Wan,

Shi

et al. 2023

Angewandte Chemie

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Multicomponent supramolecular block copolymers (BCPs) have attracted much attention due to their potential functionalities, but examples of three‐component supramolecular BCPs are rare. Herein, we report the synthesis of three‐component multiblock 1D supramolecular copolymers of Ir(III) complexes 1–3 by a sequential seeded supramolecular polymerization approach. Precise control over the kinetically trapped species via the pathway complexity of the monomers is the key to the successful synthesis of BCPs with up to 9 blocks. Furthermore, 5‐block BCPs with different sequences could be synthesized by changing the addition order of the kinetic species during a sequentially seeded process. The corresponding heterogeneous nucleation‐elongation process has been confirmed by the UV/Vis absorption spectra, and each segment of the multiblock copolymers could be characterized by both TEM and SEM. Interestingly, the energy transfer leads to weakened emission of 1‐terminated and enhanced emission of 3‐terminated BCPs. This study will be an important step in advancing the synthesis and properties of three‐component BCPs.

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Exploiting halido ligands to control nucleation pathways and Pt⋯Pt interactions in supramolecular co-polymerizations

Abstract: We use different halido ligands to tune metal-metal interactions in supramolecular polymers (SPs) of bispyridyldihalogenido PtII complexes. The different ability of chlorido vs. bromido ligands to enable Pt···Pt contacts was...

Cited by 9 publications

References 28 publications

Supramolecular Copolymers Under Kinetic, Thermodynamic, or Pathway‐Switching Control

Supramolecular Copolymers Under Kinetic, Thermodynamic, or Pathway‐Switching Control

Controlling Molecular Packing in Aqueous Metallosupramolecular Self-assembly by Ligand Geometry

Three‐Component Multiblock 1D Supramolecular Copolymers of Ir(III) Complexes with Controllable Sequences

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