Periodic Reporting for period 1 - DyeMetalloCage (Dye-Based Metallo-Supramolecular Cages for Molecular Recognition, Catalysis and Biomedical Applications)
Reporting period: 2021-09-13 to 2023-09-12
The MSCA project is concerned with the design and development of cutting-edge metallo-supramolecular assemblies based on subphthalocyanines, BODIPYs and azaBODIPYs for various applications such as molecular recognition, catalysis, and biological studies. The applications stemming from the formation of host-guest complexes within 3D capsules are diverse and impactful. These 3D architectures, creating a distinctive environment and geometric constraint, open avenues for medical applications as drug carriers, molecular recognition for selective encapsulation, and catalytic chambers or nanocontainers for reactions. Subpthalocyanines (SubPcs), with their non-planar cone-shaped conformation and inherent chirality, present unique structural and photophysical features. Additionally, the BODIPYs, a versatile fluorescent dye with excellent properties, hold promise for bioimaging, biological labelling, and fluorescence assays due to their low toxicity and high photostability. In this context, the goal of this project (DyeMetalloCage) included the investigating on advancing of SubPc and BODIPYs metallo-supramolecular cage chemistry. This project aims to bring metallo-supramolecular chemistry to unprecedented levels of applicability, developing novel water soluble assemblies constructed through supramolecular tools as new materials for technologically- and biologically relevant functions. To achieve this, we decided to devolve water soluble SubPc and BODIPYs supramolecular cages/metallocycles and investigated them for catalytic and biological applications.
Overall objectives are a) Synthesis of SubPc/azaBODIPYs ligands and their metallo-supramolecular assemblies. Standardization of synthetic route and purification technique to obtain the cages in appreciable yield; b) Investigate the ability of SubPcs metallo-supramolecular cages to serve as molecular receptors for the complexation of fullerenes and other molecules in water media. c) Assess the potential of these assemblies to create hydrophobic reaction environments in aqueous solutions, influencing and accelerating chemical reactions over fullerene species in an aqueous environment. This unexplored goal could have a significant impact on the scientific community. d) Investigate the potential of azaBODIPYs metallo-supramolecular π-amphiphiles to self-assemble into nanostructures. Explore their applications in biomedical contexts, leveraging their photosensitization capabilities for singlet oxygen generation, anticancer activity, and fluorescence properties.
Overall objectives are a) Synthesis of SubPc/azaBODIPYs ligands and their metallo-supramolecular assemblies. Standardization of synthetic route and purification technique to obtain the cages in appreciable yield; b) Investigate the ability of SubPcs metallo-supramolecular cages to serve as molecular receptors for the complexation of fullerenes and other molecules in water media. c) Assess the potential of these assemblies to create hydrophobic reaction environments in aqueous solutions, influencing and accelerating chemical reactions over fullerene species in an aqueous environment. This unexplored goal could have a significant impact on the scientific community. d) Investigate the potential of azaBODIPYs metallo-supramolecular π-amphiphiles to self-assemble into nanostructures. Explore their applications in biomedical contexts, leveraging their photosensitization capabilities for singlet oxygen generation, anticancer activity, and fluorescence properties.
WP1: Preparation of SubPc and formation of metallo-supramolecular cages (See Figure 1 of the Summary)
-Optimization of synthetic methodologies for the synthesis of 2-(pyridyl)alkynyl SubPcs and metallo-supramolecular cages.
-Development of new synthetic protocols for the synthesis of hydrophilic Pd(II) SubPc metallocages.
Outcome and significant results: Successful optimization of synthetic route to obtain higher yields of 2-(pyridyl)alkynyl SubPc and the corresponding cage.
WP2: Reactions over Fullerenes inside the capsule (See Figure 1 of the Summary)
- Optimized conditions for fullerene encapsulations in water
- Diels-Alder reaction over fullerenes: Optimization of reaction conditions such as solvent combination, temperature, time, catalyst concentration.
Outcome and significant results: First instance of a supramolecular cage serving as a catalytic molecular reactor for transformations over fullerenes in an aqueous medium
WP 3.1: Synthesis, aggregation and biological studies of metallo-supramolecular amphiphiles (See Figure 2 of the Summary)
-Optimization of the synthesis of di-pyridine azaBODIPYs precursors and azaBODIPYs-incorporated Pt(II)/Pd(II) metallo-supramolecular triangles macrocycles
- Exploration of the biological applications of Pt(II) supramolecular coordination complexes, in collaboration with Prof. Dennis K. P. Ng in Hong Kong.
Outcome and significant results: substantial advancement in the synthesis and characterization of pyridyl-functionalized azaBODIPY precursors and their incorporation into metallo-supramolecular triangles, offering valuable contributions to both fundamental understanding and potential applications in various scientific domains
WP 3.2: Synthesis, and studies of BODIPYs organic Cages (See Figure 3 of the Summary)
- Design and synthesis of enantiomeric porous organic cages through dynamic covalent chemistry, employing imine bond formation between BODIPY-based tetraaldehyde and cyclohexanediamine building blocks.
- Developing cage molecules with porous interiors, stable aromatic backbones, and multiple electron-rich building units.,
Outcome and significant results: a significant contribution to the field of organic cage chemistry, showcasing the successful implementation of dynamic covalent chemistry for the creation of organic cages with distinctive structural and spectroscopic features.
-Optimization of synthetic methodologies for the synthesis of 2-(pyridyl)alkynyl SubPcs and metallo-supramolecular cages.
-Development of new synthetic protocols for the synthesis of hydrophilic Pd(II) SubPc metallocages.
Outcome and significant results: Successful optimization of synthetic route to obtain higher yields of 2-(pyridyl)alkynyl SubPc and the corresponding cage.
WP2: Reactions over Fullerenes inside the capsule (See Figure 1 of the Summary)
- Optimized conditions for fullerene encapsulations in water
- Diels-Alder reaction over fullerenes: Optimization of reaction conditions such as solvent combination, temperature, time, catalyst concentration.
Outcome and significant results: First instance of a supramolecular cage serving as a catalytic molecular reactor for transformations over fullerenes in an aqueous medium
WP 3.1: Synthesis, aggregation and biological studies of metallo-supramolecular amphiphiles (See Figure 2 of the Summary)
-Optimization of the synthesis of di-pyridine azaBODIPYs precursors and azaBODIPYs-incorporated Pt(II)/Pd(II) metallo-supramolecular triangles macrocycles
- Exploration of the biological applications of Pt(II) supramolecular coordination complexes, in collaboration with Prof. Dennis K. P. Ng in Hong Kong.
Outcome and significant results: substantial advancement in the synthesis and characterization of pyridyl-functionalized azaBODIPY precursors and their incorporation into metallo-supramolecular triangles, offering valuable contributions to both fundamental understanding and potential applications in various scientific domains
WP 3.2: Synthesis, and studies of BODIPYs organic Cages (See Figure 3 of the Summary)
- Design and synthesis of enantiomeric porous organic cages through dynamic covalent chemistry, employing imine bond formation between BODIPY-based tetraaldehyde and cyclohexanediamine building blocks.
- Developing cage molecules with porous interiors, stable aromatic backbones, and multiple electron-rich building units.,
Outcome and significant results: a significant contribution to the field of organic cage chemistry, showcasing the successful implementation of dynamic covalent chemistry for the creation of organic cages with distinctive structural and spectroscopic features.
The results of the MSCA project are significant in many ways. The successful construction of capsules with well-defined spaces for complexing large organic guests represents a notable advancement in coordination-driven self-assembly. The project's demonstration of creating hydrophobic reaction environments in aqueous solutions is ground-breaking. This innovation not only widens the scope of accessible reactivity but also presents an ecologically friendly approach, showcasing the project's commitment to sustainable scientific practices. The ability to accelerate and potentially catalyze cycloaddition reactions over fullerene species in an aqueous environment represents an unprecedented achievement. This outcome holds significant promise for advancing the understanding of chemical reactivity in aqueous media, providing new avenues for diverse applications. The successful development of azaBODIPYs metallo-supramolecular π-amphiphiles and their self-assembly into nanostructures open new frontiers in nanotechnology and biomedicine. The successful development of dynamic covalent chemistry for the creation of enantiomeric porous BODIPY organic cages showcases a noteworthy contribution to the field of organic cage chemistry. These achievements contribute to the collective knowledge base, inspire further research, and pave the way for innovations in diverse scientific disciplines, including materials science, nanotechnology, and biomedicine. Furthermore, open access to the project’s datasets will also facilitate analysis of the data to determine the viability of new projects, which in a way will help in the optimum use of resources.