N,N,N,N-tetradentate macrocyclic ligand (L) has been synthesized by the condensation of benzil and semicarbazide and characterized. On excitation by light of wavelength 350 nm, L exhibited a fluorescent peak at λ(max) = 454 nm, which showed ca 6 times enhancement in intensity with a blue shift on interaction with Zn(2+). L has been found to act as a selective fluorescent sensor for zinc(2+) ion over a host of other metal ions such as- Cd(2+), Pb(2+), Hg(2+), Ca(2+), Fe(2+), Na(2+), Co(2+), Mn(2+), Cu(2+) and Ni(2+), in 1:1 CH(3)OH:H(2)O. A 1:1 complex formation between L and Zn(2+) was proved. The enhancement in the fluorescence could be explained on the basis of Photo induced electron transfer (PET) mechanism with log β = 1.86.
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http://dx.doi.org/10.1007/s10895-012-1046-0 | DOI Listing |
Chemistry
January 2023
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115, Bonn, Germany.
Recently, it was shown that the double Ca-H-Ca bridged calcium hydride cation dimer complex [LCaH CaL] (macrocyclic ligand L=NNNN-tetradentate Me TACD) exhibited remarkable activity in catalyzing the hydrogenation of unactivated 1-alkenes as well as the H isotope exchange under mild conditions, tentatively via the terminal Ca-H bond of cation monomer LCaH . In this DFT mechanistic work, a novel substrate-dependent catalytic mechanism is disclosed involving cooperative Ca-H-Ca bridges for H isotope exchange, competitive Ca-H-Ca bridges and terminal Ca-H bonds for anti-Markovnikov addition of unactivated 1-alkenes, and terminal Ca-H bonds for Markovnikov addition of conjugation-activated styrene. THF-coordination plays a key role in favoring the anti-Markovnikov addition while strong cation-π interactions direct the Markovnikov addition to terminal Ca-H bonds.
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