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Primogenic Effect
In inorganic chemistry, the Primogenic Effect describes the change in excited state manifolds for first row vs second and third row metal complexes. The effect is used to rationalize the ability or inability of certain metal complexes to function as photosensitizers, which in turn is relevant to photocatalysis. Complexes of the type (2,2’-bipyridine)3sup>2+ are low spin for M2+ = Fe(II), Ru(II), and Os(II). These species have similar ground state properties: they are diamagnetic and undergo reversible oxidation to the trications. As a consequence of the Primogenic Effect, the first excited state for 2+">Tris(bipyridine)iron(II) chloride"> 2+ is a Ligand field theory">ligand field state (LF state) with a Spin states (d electrons)">high spin configuration. Such LF states characteristically decay to the ground state rapidly (femtoseconds). By contrast, for [Ru(bipy)3]2+ and [Os(bipy)3]2+, the first excited state is Charge transfer band, charge-transfer in character. Bonding in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Inorganic Chemistry
Inorganic chemistry deals with chemical synthesis, synthesis and behavior of inorganic compound, inorganic and organometallic chemistry, organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, pharmaceutical drug, medications, fuels, and agriculture. Occurrence Many inorganic compounds are found in nature as minerals. Soil may contain iron sulfide as pyrite or calcium sulfate as gypsum. Inorganic compounds are also found multitasking as biomolecules: as electrolytes (sodium chloride), in energy storage (Adenosine triphosphate, ATP) or in construction (the polyphosphate backbone in DNA). Bonding Inorganic compounds exhibit a range ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Excited State
In quantum mechanics Quantum mechanics is the fundamental physical Scientific theory, theory that describes the behavior of matter and of light; its unusual characteristics typically occur at and below the scale of atoms. Reprinted, Addison-Wesley, 1989, It is ..., an excited state of a system (such as an atom, molecule or Atomic nucleus, nucleus) is any quantum state of the system that has a higher energy than the ground state (that is, more energy than the absolute minimum). Excitation refers to an increase in energy level above a chosen starting point, usually the ground state, but sometimes an already excited state. The temperature of a group of particles is indicative of the level of excitation (with the notable exception of systems that exhibit negative temperature). The lifetime of a system in an excited state is usually short: Spontaneous emission, spontaneous or stimulated emission, induced emission of a quantum of energy (such as a photon or a phonon) usually ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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, infrared radiation, Light, visible light radiation, and Ultraviolet, ultraviolet radiation and transfer absorbed energy into ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Photocatalysis
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a photocatalyst, the excited state of which "repeatedly interacts with the reaction partners forming reaction intermediates and regenerates itself after each cycle of such interactions." In many cases, the catalyst is a solid that upon irradiation with UV- or visible light generates electron–hole pairs that generate free radicals. Photocatalysts belong to three main groups; heterogeneous, homogeneous, and plasmonic antenna-reactor catalysts. The use of each catalysts depends on the preferred application and required catalysis reaction. History Early mentions (1911–1938) The earliest mention came in 1911, when German chemist Dr. Alexander Eibner integrated the concept in his research of the illumination of zinc oxide (ZnO) on the bleaching of the dark blue pigment, Prussian blue. Around this time, Bruner and Kozak published an article discussing the deterioration of oxalic acid in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
2,2’-bipyridine
The comma is a punctuation mark that appears in several variants in different languages. Some typefaces render it as a small line, slightly curved or straight, but inclined from the vertical; others give it the appearance of a miniature filled-in figure placed on the baseline. In many typefaces it is the same shape as an apostrophe or single closing quotation mark . The comma is used in many contexts and languages, mainly to separate parts of a sentence such as clauses, and items in lists mainly when there are three or more items listed. The word ''comma'' comes from the Greek (), which originally meant a cut-off piece, specifically in grammar, a short clause. A comma-shaped mark is used as a diacritic in several writing systems and is considered distinct from the cedilla. In Byzantine and modern copies of Ancient Greek, the " rough" and "smooth breathings" () appear above the letter. In Latvian, Romanian, and Livonian, the comma diacritic appears below the letter, as ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tris(bipyridine)iron(II) Chloride
Tris(bipyridine)iron(II) chloride is the chloride salt of the coordination complex tris(bipyridine)iron(II), . It is a red solid. In contrast to tris(bipyridine)ruthenium(II), this iron complex is not a useful photosensitizer because its excited states relax too rapidly, a consequence of the primogenic effect. Tris(bipyridine)iron(II) chloride features an octahedral Fe(II) center bound to three bipyridine ligand In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's el ...s. The complex has been isolated as salts with many anions. Synthesis and reactions The sulfate salt is produced by combining ferrous sulfate with excess bipy in aqueous solution. This result illustrates the preference of Fe(II) for bipyridine vs water. The potentials for , e(bipy)3sup>2+/3+ and e(phen)3sup>2+/3+ are v ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ligand Field Theory
Ligand field theory (LFT) describes the bonding, orbital arrangement, and other characteristics of coordination complexes. It represents an application of molecular orbital theory to transition metal complexes. A transition metal ion has nine valence atomic orbitals - consisting of five ''n''d, one (''n''+1)s, and three (''n''+1)p orbitals. These orbitals have the appropriate energy to form bonding interactions with ligands. The LFT analysis is highly dependent on the geometry of the complex, but most explanations begin by describing octahedral complexes, where six ligands coordinate with the metal. Other complexes can be described with reference to crystal field theory. Inverted ligand field theory (ILFT) elaborates on LFT by breaking assumptions made about relative metal and ligand orbital energies. History Ligand field theory resulted from combining the principles laid out in molecular orbital theory and crystal field theory, which describe the loss of degeneracy of metal d ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Spin States (d Electrons)
Spin states when describing transition metal coordination complexes refers to the potential spin configurations of the central metal's d electrons. For several oxidation states, metals can adopt high-spin and low-spin configurations. The ambiguity only applies to first row metals, because second- and third-row metals are invariably low-spin. These configurations can be understood through the two major models used to describe coordination complexes; crystal field theory and ligand field theory (a more advanced version based on molecular orbital theory). High-spin vs. low-spin Octahedral complexes The Ligand-field splitting parameter, Δ splitting of the Atomic orbital, ''d'' orbitals plays an important role in the electron spin state of a coordination complex. Three factors affect Δ: the period (row in periodic table) of the metal ion, the charge of the metal ion, and the field strength of the complex's ligands as described by the spectrochemical series. Only octahedral co ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Charge Transfer Band
193px, The intense color of tris(bipyridine)ruthenium(II) arises from a metal-to-ligand charge-transfer band. Charge-transfer bands are a characteristic feature of the optical spectra of many compounds. These bands are typically more intense than d–d transitions. They typically exhibit solvatochromism, consistent with shifts of electron density that would be sensitive to solvation. CT absorptions bands are intense and often lie in the ultraviolet or visible portion of the spectrum. For coordination complexes, charge-transfer bands often exhibit molar absorptivities, ε, of about 50000 L mol−1 cm−1. By contrast ε values for d–d transitions are in the range of 20–200 L mol−1 cm−1. CT transitions are spin-allowed and Laporte-allowed. The weaker d–d transitions are potentially spin-allowed but always Laporte-forbidden. Charge-transfer bands of transition metal complexes result from shift of charge density between molecular orbitals (MO) that are predominantly me ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Radical Anion
In organic chemistry, a radical anion is a free radical species that carries a negative charge. Radical anions are encountered in organic chemistry as reduced derivatives of polycyclic aromatic compounds, e.g. sodium naphthenide. An example of a non-carbon radical anion is the superoxide anion, formed by transfer of one electron to an oxygen molecule. Radical anions are typically indicated by M^. Polycyclic radical anions Many aromatic compounds can undergo one-electron reduction by alkali metals. The electron is transferred from the alkali metal ion to an unoccupied antibonding p-p п* orbital of the aromatic molecule. This transfer is usually only energetically favorable if the aprotic solvent efficiently solvates the alkali metal ion. Effective solvents are those that bind to the alkali metal cation: diethyl ether < THF < [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Atomic Orbital
In quantum mechanics, an atomic orbital () is a Function (mathematics), function describing the location and Matter wave, wave-like behavior of an electron in an atom. This function describes an electron's Charge density, charge distribution around the Atomic nucleus, atom's nucleus, and can be used to calculate the probability of finding an electron in a specific region around the nucleus. Each orbital in an atom is characterized by a set of values of three quantum numbers , , and , which respectively correspond to electron's energy, its angular momentum, orbital angular momentum, and its orbital angular momentum projected along a chosen axis (magnetic quantum number). The orbitals with a well-defined magnetic quantum number are generally complex-valued. Real-valued orbitals can be formed as linear combinations of and orbitals, and are often labeled using associated Spherical harmonics#Harmonic polynomial representation, harmonic polynomials (e.g., ''xy'', ) which describe ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemical Bonding
A chemical bond is the association of atoms or ions to form molecules, crystals, and other structures. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds or through the sharing of electrons as in covalent bonds, or some combination of these effects. Chemical bonds are described as having different strengths: there are "strong bonds" or "primary bonds" such as covalent, ionic and metallic bonds, and "weak bonds" or "secondary bonds" such as dipole–dipole interactions, the London dispersion force, and hydrogen bonding. Since opposite electric charges attract, the negatively charged electrons surrounding the nucleus and the positively charged protons within a nucleus attract each other. Electrons shared between two nuclei will be attracted to both of them. "Constructive quantum mechanical wavefunction interference" stabilizes the paired nuclei (see Theories of chemical bonding). Bonded nuclei maintain an optimal distance (t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
