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- Intensities: Spin Forbidden- Laporte Allowed- Symmetry allowed (CT)- Laporte forbidden -
- <1 ca. 250 1000-50000 20-100
- LMCT (property of metal and ligands)
- Metal: high oxidation state ligand: contain nonbonding electrons
- MLCT (property of metal and ligands)
- Metal: low ox state Ligand: haev low-lying acceptor orbitals
- Selection rules: Spin - Laporte -
- spin: must maintain spin, or transitions will be very weak. laporte- g to g is forbidden
- fluorescence
- emission btw two states of same spin multiplicity
- phosphorescence
- emission btw an excited state and ground state of diff multiplicities (diff spins) AKA luminescence!
- Internal Conversion
- non-radiative conversion between states of same spin manifold
- intersystem crossing
- non-radiative conversion btw states of different spin multiplicity
- CT Luminescence
- long lived emission occurs from states of diff multiplicty than the ground state.
- three common jahn teller cases:
- high spin d4 low spin d7 d9
- the bulkier the ligand, the...
- bigger the cone angle
- pi backbonding
- Electrons from the metal are used to bond to the ligand, in the process relieving the metal of excess negative charge.
- Fischer carbenes (4)
- singlet electron poor found with: low oxidation state metals, middle and late TM, pi electron acceptor metal ligands.
- Schrock (3)
- triplet electron rich found with: high oxidation state metals, early TM,