Related Experiment Video
Updated: Jun 12, 2025
11:54
Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles
Published on: June 25, 2018
10.3K
Pathway-dependent Metallosupramolecular Polymerization Regulated by Ligand Geometry
Papri Sutar1,2, Iván Maisuls3, Zulema Fernández1
1Universität Münster, Organisch-Chemisches Institut, Corrensstraße 36, Münster, 48149, Germany.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 24, 2024
Summary
Ligand geometry in platinum(II) complexes dictates self-assembly pathways and photophysical properties. V-shaped complexes form luminescent spherical assemblies, while linear ones yield 1D polymers.
Area of Science:
- Supramolecular chemistry
- Materials science
- Photochemistry
Background:
- Structure/property correlations are crucial for functional material development in self-assembly.
- Tuning photophysical properties and self-assembly requires precise control over molecular geometry.
Purpose of the Study:
- Investigate the impact of ligand geometry on metallosupramolecular polymerization.
- Fine-tune photophysical properties (MMLCT vs. MLCT excited states) and self-assembly pathways.
- Design and synthesize novel platinum(II) complexes with varied geometries.
Main Methods:
- Synthesis of two hydrophobic Pt(II) complexes with π-extended bidentate bipyridine ligands.
- Comparative studies of photophysical properties and self-assembly in non-polar media.
- Analysis of molecular geometry (linear vs. V-shaped) and its influence on assembly.
Main Results:
- V-shaped complex 1 forms luminescent spherical assemblies via a single-step pathway, exhibiting MMLCT states and short Pt⋅⋅⋅Pt contacts.
- Linear complex 2 self-assembles in a two-step competitive process, forming 1D polymers with slipped packing and MLCT emission.
- Ligand geometry significantly alters self-assembly behavior and excited-state characteristics.
Conclusions:
- Ligand geometry is a key design element for controlling self-assembly and photophysical properties in Pt(II) metallosupramolecular systems.
- Findings provide design guidelines for creating luminescent supramolecular assemblies.
- Expands the scope of monomers for supramolecular polymerization.
Related Concept Videos
02:51Metal-Ligand Bonds
20.6K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
20.6K
01:13Olefin Metathesis Polymerization: Overview
2.0K
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.0K
01:17Ziegler–Natta Chain-Growth Polymerization: Overview
3.2K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
3.2K
00:53Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
1.9K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
1.9K
00:57Cationic Chain-Growth Polymerization: Mechanism
2.3K
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
2.3K
01:16Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
2.5K
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
2.5K