Related Experiment Video
Updated: Aug 5, 2026
09:34
Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
Coordination-Driven Scrambling in Tricopper(I) Clusters: Thermodynamic Insights into Dynamic Assembly
Venkata Sai Sashankh Penki1, Najeeb Ullah1, Sri Sudewi2,3
1Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung80708, Taiwan.
Inorganic Chemistry
|July 27, 2026
Summary
Tricocopper(I) clusters enable control over multicomponent self-assembly by redistributing metal-ligand units. Temperature dictates whether enthalpy or entropy drives assembly, offering tunable self-sorting in dynamic combinatorial systems.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Controlling product distributions in multicomponent self-assembly is challenging, especially with pre-organized fragments.
- Metal-cluster-based dynamic combinatorial systems offer a unique approach to self-assembly.
- β-Thioketiminato tricopper(I) clusters ([LCu]3) represent a rare class of such systems.
Purpose of the Study:
- To investigate the thermodynamic control of self-assembly in heteroleptic tricopper(I) clusters.
- To understand the exchange mechanisms and temperature-dependent behavior of these dynamic systems.
- To establish a model for studying tunable self-sorting in metal-cluster systems.
Main Methods:
- Mixing homoleptic tricopper(I) clusters ([LACu]3 and [LBCu]3) to form dynamic libraries.
- Utilizing variable-temperature Nuclear Magnetic Resonance (VT-NMR) spectroscopy to study exchange dynamics.
- Employing non-linear Van't Hoff analysis and Density Functional Theory (DFT) calculations.
Main Results:
- Mixing precursors generated heteroleptic species (A2B and AB2b) with distributions following binomial statistics.
- VT-NMR confirmed rapid, reversible exchange and temperature-dependent equilibration.
- Analysis revealed a thermodynamic regime crossover near 275 K, with lower temperatures favoring enthalpy-driven homoleptic stabilization and higher temperatures favoring entropy-driven heteroleptic stabilization.
Conclusions:
- Simplified multinuclear clusters serve as effective models for exploring thermodynamic control in self-assembly.
- Temperature plays a crucial role in directing the entropic or enthalpic contributions to assembly.
- These findings provide insights into achieving tunable self-sorting in dynamic metal-cluster systems.
Related Concept Videos
01:58Cooperative Allosteric Transitions
Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
01:58Cooperative Allosteric Transitions
Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
01:58Cooperative Allosteric Transitions
Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
01:32Cytoskeletal Coordination in Cell Migration
A migrating cell changes its shape during the cyclic events of attachment and detachment from the substratum and repositions the cell organelles correspondingly. These complex events are orchestrated by the dynamic cytoskeletal network comprising actin filaments, intermediate filaments, and microtubules. Cytoskeletal crosstalk — the direct and indirect communication between the different components — is crucial for this coordination. Direct communication involves various linker proteins that...
01:45Vesicular Tubular Clusters
After budding out from the ER membrane, some COPII vesicles lose their coat and fuse with one another to form larger vesicles and interconnected tubules called vesicular tubular clusters or VTCs. These clusters constitute a compartment at the ER-Golgi interface known as ERGIC (Endoplasmic Reticulum Golgi Intermediate Compartment). The ERGIC is a mobile membrane-bound cargo transport system that sorts proteins secreted from ER and delivers them to the Golgi.
With the help of motor proteins such...
With the help of motor proteins such...
02:41Protein Complex Assembly
Proteins can form homomeric complexes with another unit of the same protein or heteromeric complexes with different types. Most protein complexes self-assemble spontaneously via ordered pathways, while some proteins need assembly factors that guide their proper assembly. Despite the crowded intracellular environment, proteins usually interact with their correct partners and form functional complexes.
Many viruses self-assemble into a fully functional unit using the infected host cell to...
Many viruses self-assemble into a fully functional unit using the infected host cell to...