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Charge-transfer bands of transition metal complexes result from shift of charge density between molecular orbitals (MO) that are predominantly metal in character and those that are predominantly ligand in character. If the transfer occurs from the MO with ligand-like character to the metal-like one, the transition is called a ligand-to-metal ...
In solution, the intensity of charge-transfer bands in the UV-Vis absorbance spectrum is strongly dependent upon the degree (equilibrium constant) of this association reaction. Methods have been developed to determine the equilibrium constant for these complexes in solution by measuring the intensity of absorption bands as a function of the ...
Once a metal complex undergoes metal-to-ligand charge transfer, the system can undergo intersystem crossing, which, in conjunction with the tunability of MLCT excitation energies, produces a long-lived intermediate whose energy can be adjusted by altering the ligands used in the complex.
This is commonly known as ligand-to-metal charge transfer or LMCT. In some cases, low-lying unoccupied ligand orbitals (π*) can receive back-donation (or backbonding) from the occupied metal orbitals. This has the opposite effect on the system, resulting in metal-to-ligand charge transfer, MLCT, and commonly appears as an additional L-edge ...
Spin crossover is commonly observed with first row transition metal complexes with a d 4 through d 7 electron configuration in an octahedral ligand geometry. [1] Spin transition curves typically plot the high-spin molar fraction against temperature. [ 3 ]
The greater stabilization that results from metal-to-ligand bonding is caused by the donation of negative charge away from the metal ion, towards the ligands. This allows the metal to accept the σ bonds more easily. The combination of ligand-to-metal σ-bonding and metal-to-ligand π-bonding is a synergic effect, as each enhances the other.
[5] [6] This electron transfer strengthens the metal–ligand bond and weakens the C–C bonds within the ligand. [7] In the case of metal-alkenes and alkynes, the strengthening of the M–C 2 R 4 and M–C 2 R 2 bond is reflected in bending of the C–C–R angles which assume greater sp 3 and sp 2 character, respectively.
Sensitizers absorb light to give redox-active excited states. For many metal-based sensitizers, excitation is realized as a metal-to-ligand charge transfer, whereby an electron moves from the metal (e.g., a d orbital) to an orbital localized on the ligands (e.g. the π* orbital of an aromatic ligand).