Photosensitizer
Photosensitizers are light absorbers that alter the course of a photochemical reaction. They usually are catalysts. They can function by many mechanisms; sometimes they abstract an electron from the substrate, and sometimes they abstract a hydrogen atom from the substrate. At the end of this process, the photosensitizer returns to its ground state, where it remains chemically intact, poised to absorb more light. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.
Theory
Mechanistic considerations
Photosensitizers absorb light and transfer the energy from the incident light into another nearby molecule either directly or by a chemical reaction. Upon absorbing photons of radiation from incident light, photosensitizers transform into an excited singlet state. The single electron in the excited singlet state then flips in its intrinsic spin state via Intersystem crossing to become an excited triplet state. Triplet states typically have longer lifetimes than excited singlets. The prolonged lifetime increases the probability of interacting with other molecules nearby. Photosensitizers experience varying levels of efficiency for intersystem crossing at different wavelengths of light based on the internal electronic structure of the molecule.Parameters
For a molecule to be considered a photosensitizer:- The photosensitizer must impart a physicochemical change upon a substrate after absorbing incident light.
- Upon imparting a chemical change, the photosensitizer returns to its original chemical form.
History
Photosensitizers have existed within natural systems for as long as chlorophyll and other light sensitive molecules have been a part of plant life, but studies of photosensitizers began as early as the 1900s, where scientists observed photosensitization in biological substrates and in the treatment of cancer. Mechanistic studies related to photosensitizers began with scientists analyzing the results of chemical reactions where photosensitizers photo-oxidized molecular oxygen into peroxide species. The results were understood by calculating quantum efficiencies and fluorescent yields at varying wavelengths of light and comparing these results with the yield of reactive oxygen species. However, it was not until the 1960s that the electron donating mechanism was confirmed through various spectroscopic methods including reaction-intermediate studies and luminescence studies.The term photosensitizer does not appear in scientific literature until the 1960s. Instead, scientists would refer to photosensitizers as sensitizers used in photo-oxidation or photo-oxygenation processes. Studies during this time period involving photosensitizers utilized organic photosensitizers, consisting of aromatic hydrocarbon molecules, which could facilitate synthetic chemistry reactions. However, by the 1970s and 1980s, photosensitizers gained attraction in the scientific community for their role within biologic processes and enzymatic processes. Currently, photosensitizers are studied for their contributions to fields such as energy harvesting, photoredox catalysis in synthetic chemistry, and cancer treatment.
Types of photosensitization processes
There are two main pathways for photosensitized reactions.Type I
In Type I photosensitized reactions, the photosensitizer is excited by a light source into a triplet state. The excited, triplet state photosensitizer then reacts with a substrate molecule which is not molecular oxygen to both form a product and reform the photosensitizer. Type I photosensitized reactions result in the photosensitizer being quenched by a different chemical substrate than molecular oxygen.Type II
In Type II photosensitized reactions, the photosensitizer is excited by a light source into a triplet state. The excited photosensitizer then reacts with a ground state, triplet oxygen molecule. This excites the oxygen molecule into the singlet state, making it a reactive oxygen species. Upon excitation, the singlet oxygen molecule reacts with a substrate to form a product. Type II photosensitized reaction result in the photosensitizer being quenched by a ground state oxygen molecule which then goes on to react with a substrate to form a product.Composition of photosensitizers
Photosensitizers can be placed into 3 generalized domains based on their molecular structure. These three domains are organometallic photosensitizers, organic photosensitizers, and nanomaterial photosensitizers.Organometallic
Organometallic photosensitizers contain a metal atom chelated to at least one organic ligand. The photosensitizing capacities of these molecules result from electronic interactions between the metal and ligand. Popular electron-rich metal centers for these complexes include Iridium, Ruthenium, and Rhodium. These metals, as well as others, are common metal centers for photosensitizers due to their highly filled d-orbitals, or high d-electron counts, to promote metal to ligand charge transfer from pi-electron accepting ligands. This interaction between the metal center and the ligand leads to a large continuum of orbitals within both the highest occupied molecular orbital and the lowest unoccupied molecular orbital which allows for excited electrons to switch multiplicities via intersystem crossing.While many organometallic photosensitizer compounds are made synthetically, there also exists naturally occurring, light-harvesting organometallic photosensitizers as well. Some relevant naturally occurring examples of organometallic photosensitizers include Chlorophyll A and Chlorophyll B.
Organic
Organic photosensitizers are carbon-based molecules which are capable of photosensitizing. The earliest studied photosensitizers were aromatic hydrocarbons which absorbed light in the presence of oxygen to produce reactive oxygen species. These organic photosensitizers are made up of highly conjugated systems which promote electron delocalization. Due to their high conjugation, these systems have a smaller gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital as well as a continuum of orbitals within the HOMO and LUMO. The smaller band gap and the continuum of orbitals in both the conduction band and the valence band allow for these materials to enter their triplet state more efficiently, making them better photosensitizers. Some notable organic photosensitizers which have been studied extensively include benzophenones, methylene blue, rose Bengal, flavins, pterins and others.Nanomaterials
A wide variety of nanomaterials function as photosensitizers.Monatomic gaseous mercury is a photosensitizer catalyzing radical dehydrogenation.