Photophysical Rate Constants and Oxygen Dependence for Si and Ge Rhodamine Zwitterions.

The family of group XIV rhodamine zwitterions are fluorescence probes with carbon, silicon, germanium, or tin substituted in the 10-position of the xanthene ring. Because of their inherent near-infrared fluorescence, photostability and high quantum yields in aqueous solutions, the Si and Ge containing fluorophores in this class have become increasingly important for fluorescent labeling of proteins and biological molecules. This study fully characterizes photophysical rates derived from a model consisting of a singlet ground state, the lowest singlet excited state, and the lowest triplet excited state for two exemplar group XIV rhodamine zwitterions, one containing Si and the other Ge. Within a simple Jablonski diagram, all radiative and non-radiative rates, including intersystem crossing and triplet depopulation rates, were measured as a function of oxygen concentration. It was shown that the triplet depopulation rates are intrinsically fast in comparison with traditional xanthene containing fluorophores, probably due to the increased spin-obit coupling from the Si and Ge substitution in the xanthene ring. Dissolved oxygen increases both the intersystem crossing and triplet depopulation rates. Stern-Volmer analysis was conducted to estimate rates of quenching by oxygen. The experimental data was used to estimate the initial rates for reactive oxygen production by Si and Ge containing fluorophores in aqueous solutions containing different concentrations of dissolved O2. These estimates showed a significantly slower initial rate of reactive oxygen production in comparison with rhodamine 6G. This goes a long way to explaining their inherent photostability. Spectroscopic experiments were also conducted in 77 K viscous aqueous glasses where it was observed that the fluorescence spectra remained unchanged, and the quantum yields increased from 0.53 to 0.84 and from 0.52 to 0.89 for the Si and Ge containing fluorophores respectively; no phosphorescence was observed. All intersystem crossing and triplet depopulation rates were measured using fluorescence correlation spectroscopy (FCS) and analyzed using a new method that extrapolated the power dependence of the FCS curves to optical saturation. This method was verified using published data.

Alkynyl Linkers as a Design Tool to Gain Control over the Self-Assembly of Meso-Substituted Porphyrins on HOPG.

Self-assembled monolayers (SAMs) fall generally into two broad categories: those that are covalently bound either to the surface or to each other and those that rely on weaker forces such as hydrogen bonding or van der Waals forces. The engineering of the structure of SAMs formed from weaker forces is an exciting and complex field that often utilizes long alkane substituents bound to core moieties. The core provides the unique optical, electronic, or catalytic property desired, while the interdigitation of the alkane chains provides the means for creating well-regulated patterns of cores on the substrate. This design technique sometimes fails because some of the alkane substituents remain extended into solution rather than become interdigitated on the substrate. One contributor to this is steric hindrance between elements of the core and of the alkane chain. It is shown that the use of an alkyne linker between the core and the alkane chain can, in the case of meso-substituted porphyrins, significantly reduce this steric barrier and allow more stable and predictable surface structures to form. In particular, 5,15-bis(1-octynyl)porphyrin and 5,15-bis(1-tetradecynyl)porphyrin are shown to form significantly more stable SAMs than their alkane-linked counterparts. Scanning tunneling microscopy is used to provide detailed surface structures. Temperature and solution concentration dependence of the surface coverage is also reported. Density functional theory (DFT) is used to determine the energetic effects associated with alkane substitution at both the meso and ß positions and the beneficial energetic effects of the alkyne linker.

Synthesis of N-Substituted 3-Amino-4-halopyridines: A Sequential Boc-Removal/Reductive Amination Mediated by Brønsted and Lewis Acids.

N-Substituted 3-amino-4-halopyridines are valuable synthetic intermediates, as they readily provide access to imidazopyridines and similar heterocyclic systems. The direct synthesis of N-substituted 3-amino-4-halopyridines is problematic, as reductive aminations and base-promoted alkylations are difficult in these systems. A high yielding deprotection/alkylation protocol mediated by trifluoroacetic acid and trimethylsilyl trifluoromethanesulfonate is described, providing access to a wide scope of N-substituted 3-amino-4-halopyridines. This protocol furnishes many reaction products in high purity without chromatography. Similar reductive amination conditions were also established for deactivated anilines.