Assembly of a Highly Stable Luminescent Zn5 Cluster and Application to Bio-Imaging.

The assembly sequence of the coordination cluster [Zn5 (H2 L(n) )6 ](NO3 )4 ]⋅8 H2 O⋅2 CH3 OH (Zn5 , H3 L(n) =(1,2-bis(benzo[d]imidazol-2-yl)-ethenol) involves in situ dehydration of 1,2-bis(benzo[d]imidazol-2-yl)-1,2-ethanediol (H4 L) through the formation of the [Zn(H3 L)2 ](+) monomer, dimerization to [Zn2 (H3 L)2 ](+) , dehydration of the ligand to [Zn2 (H2 L(n) )2 ](+) , and the final formation of the pentanuclear cluster. The cluster has the following special characteristics: 1) high stability in both refluxing 37 % HCl and 27 % NH3 , 2) low cytotoxicity, and 3) pH-sensitive fluorescence in the visible-to-near-infrared (Vis/NIR) region in the solid state and in solution. We have applied it as a fluorescent probe both in vivo and in vitro. Its H-bonding ability is the key to its affinity and selectivity for imaging lysosomes in HeLa cells and tumors in male BALB/C mice. It provides a new type of sensitive and biocompatible fluorescent probe for detecting small tumors (13.5 mm(3) ).

Microwave versus traditional solvothermal synthesis of Ni7(II) discs: effect of ligand on exchange reaction in solution studied by electrospray ionization-mass spectroscopy and magnetic properties.

A comparative evaluation of the solvothermal method of synthesis of magnetic Ni(7) discs with four different ligands using the same concentrations of reagents and temperature found microwave heating is more effective than the traditional oven one. Where the former only needs minutes, the latter needs days with an equivalence of 10 min microwave to 1 day of traditional. The size of crystals has a narrow distribution and increases with time for the microwave but is a rather wide distribution for the traditional one. Furthermore the shape of the crystals is more regular for the microwave. The four Ni(7)(II) discs of formulas [Ni(7)L(6)(µ(3)-OMe)(6)](ClO(4))(2) (1-3) and {[Ni(7)(L(4))(6)(µ(3)-OMe)(6)][Ni(L(4))(2)]}(ClO(4))(2) (4) were synthesized as green hexagonal rods from Ni(ClO(4))(2)·6H(2)O in mixed MeOH/MeCN solution and salicylalde Schiff base ligands (L(1) = 2-methoxy-6-(iminomethyl)phenol, L(2) = 2-ethoxy-6-(iminomethyl)phenol, L(3) = 2-methoxy-6-((methylimino)methyl)phenol, L(4) = 2-ethoxy-6-((methylimino)methyl)phenol). X-ray structural analyses show six symmetrically positioned Ni(2) around a central Ni(1) bridged by the µ(3)-methoxide and surrounded by the ligand L which also isolates the discs from one another. The perchlorate sits in the interstices, and the planar [Ni(L(4))(2)] of 4 also inserts itself between the discs. The structures of 1-3 can be regarded as ordered discotic liquid crystals. Electrospray ionization mass spectrometry of solutions showed an exchange of methoxide for hydroxide and a different distribution of [Ni(7)] phase with mixed (MeO/OH) core bridges, confirming a probable "step by step" substitution of MeO(-) by OH(-). Magnetic studies indicate ferromagnetic interaction between Ni(1) and Ni(2) and possible antiferromagnetic between Ni(2) and Ni(2), resulting in a noncollinear system which only reaches half of the moment in 50 kOe at 2 K.