First isolation of disubstituted cis-5,6-dihydro-1,10-phenanthrolines. Lipase-mediated resolution of cis- and trans-phenoxy alcohol isomers and assignment of absolute stereochemistry via CD and NMR spectroscopy.

5,6-Dihydro-1,10-phenanthrolines can display axial and central chirality. In conjunction with the ligating properties of the diimino moiety, this class of compounds is of great interest to applications in supramolecular chemistry. We report the first preparation of cis-5,6-dihydro-1,10-phenanthroline derivatives by reacting triphenyl borate with the corresponding epoxide precursor. We found that solvent and temperature choice determined the stereoselectivity of the epoxide opening giving rise to the cis (14:1 dr) or trans (99:1 dr) product. Racemates of each stereoisomeric mixture, cis- and trans-phenoxy alcohol, were separated via highly enantioselective transesterifications with lipase PSCI from Burkholderia cepacia (97% ee, E > 200). Stereochemical assignments were carried out using CD and X-ray analyses in conjunction with NMR studies of α-methoxy-α-(trifluoromethyl)phenylacetic acid and α-methoxyphenylacetic acid esters.

Single- and multiphoton turn-on fluorescent Fe(3+) sensors based on bis(rhodamine).

Selective and sensitive turn-on fluorescent Fe(3+) sensors based on novel bis(rhodamine) dye molecules are reported. The compounds are synthesized with very high yields and characterized with NMR, ESI mass spectrometry, and elemental analysis. Single- and two-photon fluorescence enhancement is observed for both molecules in the presence of Fe(3+). High selectivity and sensitivity is observed over other metal ions and is shown to be due mainly to the spirolactam ring-opening power of Fe(3+). All measurements are made in buffer environments simulating biological conditions to facilitate single- and multiphoton fluorescence imaging of Fe(3+) in vivo and in vitro. Larger enhancement of fluorescence for both one- and two-photon excitation makes them suitable candidates for fluorescent labeling of biological systems. Two photon cross-section and time-resolved fluorescence measurements are utilized to understand the selectivity of the present sensors for Fe(3+)-sensing.