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LMCT
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 ...
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Coordination Complex
A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of chemical bond, bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many metal-containing chemical compound, compounds, especially those that include transition metals (elements like titanium that belong to the periodic table's d-block), are coordination complexes. Nomenclature and terminology Coordination complexes are so pervasive that their structures and reactions are described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor atoms, which can be the same or different. A Ligand#Polydentate and polyhapto ligand motifs and nomenclature, polydentate (multiple bonded) ligand is a molecule or ion that bonds to the central atom ...
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Tris(bipyridine)ruthenium(II)-chloride-powder
Tris, or tris(hydroxymethyl)aminomethane, or known during medical use as tromethamine or THAM, is an organic compound with the formula (HOCH2)3CNH2. It is extensively used in biochemistry and molecular biology as a component of buffer solutions such as in TAE buffer, TAE and TBE buffers, especially for solutions of nucleic acids. It contains a primary amine and thus undergoes the reactions associated with typical amines, e.g., condensations with aldehydes. Tris also complexes with metal ions in solution. In medicine, tromethamine is occasionally used as a drug, given in intensive care for its properties as a buffer for the treatment of severe metabolic acidosis in specific circumstances. Some medications are formulated as the "tromethamine salt" including Hemabate (carboprost as trometamol salt), and "ketorolac trometamol". In 2023 a strain of ''Pseudomonas hunanensis'' was found to be able to degrade TRIS buffer. Since Tris' pKa is more strongly temperature dependent, its use is ...
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Solvatochromism
In chemistry, solvatochromism is the phenomenon observed when the colour of a solution is different when the solute is dissolved in different solvents. The solvatochromic effect is the way the spectrum of a substance (the solute) varies when the substance is dissolved in a variety of solvents. In this context, the dielectric constant and hydrogen bonding capacity are the most important properties of the solvent. With various solvents there is a different effect on the electronic ground state and excited state of the solute, so that the size of energy gap between them changes as the solvent changes. This is reflected in the absorption or emission spectrum of the solute as differences in the position, intensity, and shape of the spectroscopic bands. When the spectroscopic band occurs in the visible part of the electromagnetic spectrum, solvatochromism is observed as a change of colour. This is illustrated by Reichardt's dye, as shown in the image. Negative solvatochromism co ...
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Laporte Rule
The Laporte rule is a rule that explains the intensities of absorption spectra for chemical species. It is a selection rule that rigorously applies to atoms, and to molecules that are centrosymmetric, i.e. with an inversion centre. It states that electronic transitions that conserve parity are forbidden. Thus transitions between two states that are each symmetric with respect to an inversion centre will not be observed. Transitions between states that are antisymmetric with respect to inversion are forbidden as well. In the language of symmetry, ''g'' (gerade = even (German)) → ''g'' and ''u'' (ungerade = odd) → ''u'' transitions are forbidden. Allowed transitions must involve a change in parity, either ''g'' → ''u'' or ''u'' → ''g''. For atoms s and d orbitals are gerade, and p and f orbitals are ungerade. The Laporte rule implies that s to s, p to p, d to d, etc. transitions should not be observed in atoms or centrosymmetric molecules. Practically speaking, only d-d t ...
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Molecular Orbitals
In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The terms ''atomic orbital'' and ''molecular orbital'' were introduced by Robert S. Mulliken in 1932 to mean ''one-electron orbital wave functions''. At an elementary level, they are used to describe the ''region'' of space in which a function has a significant amplitude. In an isolated atom, the orbital electrons' location is determined by functions called atomic orbitals. When multiple atoms combine chemically into a molecule by forming a valence chemical bond, the electrons' locations are determined by the molecule as a whole, so the atomic orbitals combine to form molecular orbitals. The electrons from the constituent atoms occupy the molecular orbitals. Mathematically, molecular orbitals are an ...
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Permanganate Spectrum
A permanganate () is a chemical compound with the manganate(VII) ion, , the conjugate base of permanganic acid. Because the manganese atom has a +7 oxidation state, the permanganate(VII) ion is a strong oxidising agent. The ion is a transition metal oxo complex, transition metal ion with a tetrahedral molecular geometry, tetrahedral structure. Permanganate solutions are purple in colour and are stable in pH, neutral or slightly alkaline media. Production Permanganates can be produced by oxidation of manganese compounds such as manganese chloride or manganese sulfate by strong oxidizing agents, for instance, sodium hypochlorite or lead dioxide: :2 MnCl2 + 5 NaClO + 6 NaOH → 2 NaMnO4 + 9 NaCl + 3 H2O :2 MnSO4 + 5 PbO2 + 3 H2SO4 → 2 HMnO4 + 5 PbSO4 + 2 H2O It may also be produced by the disproportionation of manganates, with manganese dioxide as a side-product: :3 Na2MnO4 + 2 H2O → 2 NaMnO4 + MnO2 + 4 ...
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Tris(bipyridine)ruthenium(II) Chloride
Tris(bipyridine)ruthenium(II) chloride is the chloride salt coordination complex with the formula [Ru(bpy)3]Cl2. This polypyridine complex is a red crystalline salt obtained as the water of crystallization, hexahydrate, although all of the properties of interest are in the cation [Ru(bpy)3]2+, which has received much attention because of its distinctive optical properties. The chlorides can be replaced with other anions, such as hexafluorophosphate, PF6−. Synthesis and structure image:RuCl2(bipy)2.png, left, 144px, Cis-Dichlorobis(bipyridine)ruthenium(II), ''cis''-Dichlorobis(bipyridine)ruthenium(II) is an intermediate in the synthesis of tris(bipyridine)ruthenium(II) chloride. This salt is prepared by treating an aqueous solution of ruthenium trichloride with 2,2'-bipyridine. In this conversion, Ru(III) is reduced to Ru(II), and hypophosphorous acid is typically added as a reducing agent. [Ru(bpy)3]2+ is octahedral, containing a central low spin d6 Ru(II) ion and three biden ...
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Pigment Berliner Blau
A pigment is a powder used to add or alter color or change visual appearance. Pigments are completely or nearly insoluble and chemically unreactive in water or another medium; in contrast, dyes are colored substances which are soluble or go into solution at some stage in their use. Dyes are often organic compounds whereas pigments are often inorganic. Pigments of prehistoric and historic value include ochre, charcoal, and lapis lazuli. Economic impact In 2006, around 7.4 million tons of inorganic, organic, and special pigments were marketed worldwide. According to an April 2018 report by ''Bloomberg Businessweek'', the estimated value of the pigment industry globally is $30 billion. The value of titanium dioxide – used to enhance the white brightness of many products – was placed at $13.2 billion per year, while the color Ferrari red is valued at $300 million each year. Physical principles Like all materials, the color of pigments arises because they absorb o ...
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Intervalence Charge Transfer
192 px, The intense blue color of Prussian blue is a consequence of an intervalence charge transfer band. In chemistry, intervalence charge transfer, often abbreviated IVCT or even IT, is a type of charge-transfer band that is associated with mixed valence compounds. It is most common for systems with two metal sites differing only in oxidation state. Quite often such electron transfer reverses the oxidation states of the sites. The term is frequently extended to the case of metal-to-metal charge transfer between non-equivalent metal centres. The transition produces a characteristically intense absorption in the electromagnetic spectrum. The band is usually found in the visible or near infrared Infrared (IR; sometimes called infrared light) is electromagnetic radiation (EMR) with wavelengths longer than that of visible light but shorter than microwaves. The infrared spectral band begins with the waves that are just longer than those ... region of the spectrum and is broad ...
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Mixed-valence Compound
Mixed valence complexes contain an element which is present in more than one oxidation state. Well-known mixed valence compounds include the Creutz–Taube complex, Prussian blue, and molybdenum blue. Many solids are mixed-valency including indium chalcogenides. Robin–Day classification Mixed-valence compounds are subdivided into three groups, according to the Robin–Day classification: *Class I, where the valences are trapped—localized on a single site—such as Pb3O4 and antimony tetroxide. There are distinct sites with different specific valences in the complex that cannot easily interconvert. *Class II, which are intermediate in character. There is some localization of distinct valences, but there is a low activation energy for their interconversion. Some thermal activation is required to induce electron transfer from one site to another via the bridge. These species exhibit an intense Intervalence charge transfer (IT or IVCT) band, a broad intense absorption i ...
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Infrared
Infrared (IR; sometimes called infrared light) is electromagnetic radiation (EMR) with wavelengths longer than that of visible light but shorter than microwaves. The infrared spectral band begins with the waves that are just longer than those of red light (the longest waves in the visible spectrum), so IR is invisible to the human eye. IR is generally (according to ISO, CIE) understood to include wavelengths from around to . IR is commonly divided between longer-wavelength thermal IR, emitted from terrestrial sources, and shorter-wavelength IR or near-IR, part of the solar spectrum. Longer IR wavelengths (30–100 μm) are sometimes included as part of the terahertz radiation band. Almost all black-body radiation from objects near room temperature is in the IR band. As a form of EMR, IR carries energy and momentum, exerts radiation pressure, and has properties corresponding to both those of a wave and of a particle, the photon. It was long known that fires e ...
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