Electron delocalization in the S1 and T1 metal-to-ligand charge transfer states of trans-substituted metal quadruply bonded complexes.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 21525414.
- Also identified by DOI 10.1073/pnas.1103082108 and PMC identifier 3100943.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
The singlet S(1) and triplet T(1) photoexcited states of the compounds containing MM quadruple bonds trans-M(2)(T(i)PB)(2)(O(2)CC(6)H(4)-4-CN)(2), where T(i)PB = 2,4,6-triisopropylbenzoate and M = Mo (I) or M = W (I(')), and trans-M(2)(O(2)CMe)(2)((N[(i) Pr ])(2)CC ≡ CC(6)H(5))(2), where M = Mo (II) and M = W (II(')), have been investigated by a variety of spectroscopic techniques including femtosecond time-resolved infrared spectroscopy. The singlet states are shown to be delocalized metal-to-ligand charge transfer (MLCT) states for I and I(') but localized for II and II(') involving the cyanobenzoate or amidinate ligands, respectively. The triplet states are MoMoδδ* for both I and II but delocalized (3)MLCT for I(') and localized (3)MLCT for II('). These differences arise from consideration of the relative orbital energies of the M(2)δ or M(2)δ* and the ligand π(∗) as well as the magnitudes of orbital overlap.