RESUMO
Nitrated polycyclic molecules can present the largest singlet-triplet crossing rates among organic molecules. This implies that most of these compounds have no detectable steady-state fluorescence. In addition, some nitroaromatics undergo a complex series of photoinduced atom rearrangements that result in nitric oxide dissociation. The overall photochemistry of these systems depends critically on the competition between the rapid intersystem crossing channel and other excited-state pathways. In this contribution, we sought to characterize the degree of stabilization of the S1 state due to solute-solvent interactions, and to quantify the effect of such stabilization on their photophysical pathways. We studied 2- and 4-nitropyrene (2-NP and 4-NP), which are atypically emissive nitroaromatics in a series of solvents. From steady-state and time-resolved measurements, the S1 state of these molecules shows significant stabilization as the solvent polarity is increased. On the other hand, specific triplet states that are iso-energetic with the emissive singlet (T3 for 2-NP and T2 for 4-NP) in nonpolar solvents become slightly de-stabilized upon increasing the solvent polarity. These combined effects result in rapid singlet-triplet population transfer in nonpolar solvents for both molecules. In contrast, for solvents with even slightly higher polarities, the first excited singlet is stabilized in relation to the specific triplet states, leading to much longer S1 lifetimes. These effects can be summarized as a highly solvent-dependent coupling/decoupling of the manifolds. Similar effects are also likely to be present in other nitroaromatics where there is a dynamic competition between nitric oxide dissociation and intersystem crossing. The drastic effects of the solvent polarity in the manifold crossing pathway should be taken into consideration in both theoretical and experimental studies of nitroaromatics.
RESUMO
We have designed and synthesized two new cyaninic Nd3+ complexes where the lanthanide emission can be induced from simultaneous two-photon absorption followed by energy migration. These complexes correspond to a molecular design that uses an antenna ligand formed by the functionalization of a heptamethine dye with 5-ol-phenanthroline or 4-phenyl-terpyridine derivatives. These complexes employ the important nonlinear optical properties of symmetric polymethines to sensitize the lanthanide ion. We verified that simultaneous biphotonic excitation indirectly induces the 4F3/2 â 4I11/2 Nd3+ emission using femtosecond laser pulses tuned below the first electronic transition of the antenna. The simultaneous two-photon excitation events initially form the nonlinear-active second excited singlet of the polymethine antenna, which rapidly evolves into its first excited singlet. This state in turn induces the formation of the emissive Nd3+ states through energy transfer. The role of the first excited singlet of the antenna as the donor state in this process was verified through time resolution of the antenna's fluorescence. These measurements also provided the rates for antenna-lanthanide energy transfer, which indicate that the phenanthroline-type ligand is approximately five times more efficient for energy transfer than the phenyl-terpyridine derivative due to their relative donor-acceptor distances. The simultaneous two-photon excitation of this polymethine antenna allows for high spatial localization of the Nd3+excitation events.
RESUMO
A chelating coumarin-derived ligand sensitizes all emitting lanthanide ions in the solid state and gives high absolute quantum yields for ethanol solutions of complexes of Sm, Eu, Tb, and Dy, above 20% for the last two. Crystal structures of these four complexes are [Ln(Cum)3(H2O)(X)]·X where X = MeOH or EtOH.
