Aggregation-enhanced IR absorption (AEIRA) of molybdenum-carbonyl organometallic aqueous colloids

作者：Murshid Nimer; Rahman Mohammad A; Wang Xiaosong^*

来源：Journal of Organometallic Chemistry, 2016, 819: 109-114.

DOI：10.1016/j.jorganchem.2016.06.031

• Aggregation-enhanced IR absorption (AEIRA)
• Organometallic nanovesicles
• MCsomes
• Water-carbonyl interaction (WCI)
• Molybdenum-carbonyl complex
• Migration insertion reaction

Molybdenum-carbonyl aqueous colloids are prepared from the self-assembly of eta(5)-CpMo(CO)(2)(PPh3) CO(CH2)(5)CH3 (MpC6) in water. MpC6 is synthesized through a reaction of CpMo(CO)(3) anion (Mp(-)) with Br(CH2)(5)CH3 in the presence of PPh3. The complex is characterized using IR, H-1 NMR, P-31 NMR spectroscopies and confirmed by X-ray crystallography. MpC6 is hydrophobic, non-surface active, but capable of assembling in water without critical aggregation concentration (CAC) via water carbonyl interactions (WCIs). The assembly generates vesicles with a zeta potential of -69.6 mV and the resultant colloids possess a highly integrated structure upon dilution. The hydrodynamic radius (R-h) of the colloids is ca. 60 nm with a narrow size distribution (PDI = 0.07). The IR absorption of the CO groups for the aggregates in THF/water (40/60 v/v) solution is similar to 70-fold stronger than that for the MpC6 molecules in THF. This aggregation-enhanced IR absorption (AEIRA) is attributed to the association of the polarizable metal carbonyl groups on the surface of the colloids.

• 出版日期2016-9-15