Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S1 state is the only significant product of the radiationless decay of the S2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

Determinants of the efficiency of photon upconversion by triplet-triplet annihilation in the solid state: zinc porphyrin derivatives in PVA.

Spectroscopic, photophysical and computational studies designed to expose and explain the differences in the efficiencies of non-coherent photon upconversion (NCPU) by triplet-triplet annihilation (TTA) have been carried out for a new series of alkyl-substituted diphenyl and tetraphenyl zinc porphyrins, both in fluid solution and in solid films. Systematic variations in the alkyl-substitution of the phenyl groups in both the di- and tetraphenyl porphyrins introduces small, but well-understood changes in their spectroscopic and photophysical properties and in their TTA efficiencies. In degassed toluene solution TTA occurs for all derivatives and produces the fluorescent S2 product states in all cases. In PVA matrices, however, none of the di-phenylporphyrins exhibit measurable NCPU whereas all the tetraphenyl-substituted compounds remain upconversion-active. In PVA the NCPU efficiencies of the zinc tetraphenylporphyrins vary significantly with their steric characteristics; the most sterically crowded tetraphenyl derivative exhibits the greatest efficiency. DFT-D computations have been undertaken and help reveal the sources of these differences.

White light generation using Förster resonance energy transfer between 3-hydroxyisoquinoline and Nile Red.

Simple composite films consisting of a polymer blended with organic emitters have the potential for broad-band "white" light emission that can be used for general lighting applications. In the present work, a simple mixture of 3-hydroxyisoquinoline (HIQ) with Nile Red (NR) in a polymeric matrix of polyvinyl alcohol (PVA) is used to generate white light through a non-radiative excitation energy transfer (NREET) mechanism. NREET between HIQ and NR doped in PVA films is investigated using a combination of steady state and time resolved fluorescence spectroscopic methods. It is observed that NR has very weak fluorescence in the PVA film upon excitation at 400 nm, but upon mixing NR with HIQ, sensitized emission of NR is observed with decreased emission of HIQ. The behavior of the sensitized emission of NR is consistent with Förster resonance energy transfer (FRET) between the donor HIQ and acceptor NR. By adjusting the relative fractions of HIQ and NR in the films, the extent of FRET could be regulated and the overall film emission color could be manipulated to enable overall "white" (CIE color coordinates 0.34, 0.38) emission. The films showed excellent photostability with 405 nm diode illumination, along with mechanical flexibility, suggesting good potential utility as a down converting element for lighting applications.

Spectroscopic and Structural Studies of a Surface Active Porphyrin in Solution and in Langmuir-Blodgett Films.

Controlling aggregation of the dual sensitizer-emitter (S-E) zinc tetraphenylporphyrin (ZnTPP) is an important consideration in solid state noncoherent photon upconversion (NCPU) applications. The Langmuir-Blodgett (LB) technique is a facile means of preparing ordered assemblies in thin films to study distance-dependent energy transfer processes in S-E systems and was used in this report to control the aggregation of a functionalized ZnTPP on solid substrates. This was achieved by synthetic addition of a short polar tail to one of the pendant phenyl rings in ZnTPP in order to make it surface active. The surface active ZnTPP derivative formed rigid films at the air-water interface and exhibited mean molecular areas consistent with approximately vertically oriented molecules under appropriate film compression. A red shift in the UV-vis spectra as well as unquenched fluorescence emission of the LB films indicated formation of well-ordered aggregates. However, NCPU, present in the solution phase, was not observed in the LB films, suggesting that NCPU from ZnTPP as a dual S-E required not just a controlled aggregation but a specific orientation of the molecules with respect to each other.

Photochemistry and excited state prototropic behaviour of 8-amino 2-naphthol.

In the present work, photophysical behaviour of 8-amino 2-naphthol in various solvents as well as at various pH values has been investigated. Various ground and excited state species are noticed. It exhibits a completely different photo prototropic behaviour as compared to its parent molecule 2-naphthol. The spectral and transient studies indicate that at lower pH values, equilibrium between cation and neutral exists in the excited state. At neutral pH some peculiar behaviour in its spectral properties is noticed.

Fluorescence characteristics of 5-amino salicylic acid: An iodide recognition study.

In this paper we report the effect of iodide on the fluorescence of 5-amino salicylic acid (5-ASA). In the absence of iodide, prominent blue green (BG) emission band at ∼465nm (broad) is observed in aprotic solvents whereas violet (V) emission at ∼408nm, blue green (BG) at ∼480nm and green (G) at ∼500nm are observed in case of protic solvents. On the addition of iodide ion (I(-)), the intensity of BG fluorescence is enhanced in case of aprotic solvents. On the other hand the G band is enhanced in protic solvents and decrease in the intensity of the V band is observed. The effect of hydrogen bonding as well as the interplay of neutral and ionic species is invoked to explain the observed results. The study projects the application of this system in iodide recognition in protic/aprotic environments.