Introduction of plumbole to f-element chemistry.
Luca MünzfeldXiaofei SunSören SchlittenhardtChristoph SchooAdrian HauserSebastian GillhuberFlorian WeigendMario RubenPeter W RoeskyPublished in: Chemical science (2021)
Herein, we present the synthesis and characterization of heteroleptic lanthanide complexes bearing a dianionic η 5 -plumbole ligand in their coordination sphere. The reaction proceeds via a salt elimination reaction between the dilithioplumbole ([Li(thf)] 2 [1,4-bis- tert -butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl] = [Li 2 (thf) 2 (η 5 -L Pb )]) and specifically designed [Ln(η 8 -COT TIPS )BH 4 ] precursors (Ln = lanthanide, La, Ce, Sm, Er; COT TIPS = 1,4-bis-triisopropylsilyl-cyclooctatetraenyl), that are capable of stabilizing a planar plumbole moiety in the coordination sphere of different trivalent lanthanide ions. In-depth ab initio calculations show that the aromaticity of the dianionic plumbole is retained upon coordination. Electron delocalization occurs from the plumbole HOMO to an orbital of mainly d-character at the lanthanide ion. The magnetic properties of the erbium congener were investigated in detail, leading to the observation of magnetic hysteresis up to 5 K (200 Oe s -1 ), an unequivocal proof for single molecule magnet behavior in this system. The magnetic behavior of the erbium species can be modulated by manipulating the position of the lithium cation in the complex, which directly influences the bonding metrics in the central [(η 5 -L Pb )Er(η 8 -COT TIPS )] - fragment. This allowed us to assess a fundamental magneto-structural correlation in an otherwise identical inner coordination sphere.
Keyphrases
- single molecule
- atomic force microscopy
- ionic liquid
- molecularly imprinted
- living cells
- heavy metals
- energy transfer
- aqueous solution
- solid state
- estrogen receptor
- metal organic framework
- quantum dots
- molecular dynamics
- breast cancer cells
- endoplasmic reticulum
- ion batteries
- molecular dynamics simulations
- mass spectrometry
- risk assessment