Kenneth P. Ghiggino

The photophysics of rhodamine B

Abstract The effects of solvent viscosity and dielectric constant on the photophysics of rhodamine B in its protonated and zwitterion forms were studied. The internal conversion rate is dependent on the S 1 -S 0 energy separation and increases when this gap is lowered through rotation of the diethylamino groups. Comparison is made with rhodamine 640 in which torsional motion about the C—N bond is not possible.

Rate expressions for excitation transfer. II. Electronic considerations of direct and through–configuration exciton resonance interactions

The electronic interactions which promote singlet–singlet and triplet–triplet electronic excitation (energy) transfer (EET) are investigated in detail. Donor and acceptor locally excited configurations, ψ1(A*B) and ψ4(AB*), respectively, are each allowed to mix with bridging ionic configurations, ψ2(A+B−) and ψ3(A−B+) to form the new donor and acceptor wave functions ΨR=ψ1+λψ2+μψ3 and ΨP=ψ4+μψ2+λψ3. Use of the latter wave functions leads to the establishment of the matrix element TRP= 〈ΨR‖H−E1‖ΨP〉≊T14−(T12T24+T 13T34)/A, with Tij=〈ψi‖H−E1‖ψj〉 and A=E2−E1, as the exciton resonance interaction term for EET. Introduction of the Mulliken approximation shows that the ‘‘direct’’ exciton resonance interaction term (T14) contributes primarily a Coulombic interaction, for singlet–singlet EET, while the ‘‘through–configuration’’ exciton resonance interaction term [−(T12T24+T13T34)/A] replaces the Dexter exchange integral (which is a component of H14) as the primary source of short‐range orbital overlap‐dependent EE...

Spectroscopy of Naphthalene Diimides and Their Anion Radicals

Naphthalene diimides 1–4 having different N,N-disubstitution undergo single electron reduction processes either chemically or electrochemically to yield the corresponding radical anion in high yield. This study concentrates on 1, bearing pentyl side chains connected through the diimide nitrogens, and compares the results obtained against those bearing isopropyl, propargyl, and phenylalanyl side chains. Compound 1 exhibits mirror image absorption and fluorescence in the near-UV region in CH2Cl2 and dimethylformamide that is typical of monomeric N,N-dialkyl-substituted naphthalene diimides. In toluene, excimer-like emission is observed, which suggests ground-state complexes involving 1 are formed. X-Ray crystallography has been used to characterize 1 in the solid state. Cyclic voltammetry enables the reversible potentials for [NDI]0/– and [NDI]−/2– type processes to be measured. Bulk one-electron reduction of 1–4 is characterized by dramatic changes in the absorption and emission spectra. Additionally, highly structured EPR (electron paramagnetic resonance) signals from dimethylformamide solutions of the radical anions of 1–3 have been obtained and are consistent with coupling between the unpaired electron and the naphthalene diimide nitrogens and hydrogens and the NCH hydrogens of the appropriate side chains. The overall structure of the EPR spectrum is substituent-dependent. These changes in spectroscopic output upon an electronic input may be described as a simple ‘on/off’ switching mechanism with which to apply a ‘bottom-up’ approach to molecular device manufacture.

Rate expressions for excitation transfer. III. An ab initio study of electronic factors in excitation transfer and exciton resonance interactions

A detailed theory for electronic aspects of electronic excitation (energy) transfer (EET) for sandwich dimers was derived in paper II of this series [J. Chem. Phys. 101, 10 521 (1994)]. In II, the electronic transfer matrix element for EET was evaluated, then simplified to various levels of approximation. The results of ab initio molecular orbital calculations on an ethene sandwich dimer are reported here in order to test and quantify the theory of II. The calculations were undertaken using a STO‐6G basis set and localized molecular orbitals, with separations of 4, 5, and 6 A between the molecules. It is demonstrated that the important electronic factors contributing to EET are the Coulombic interaction (for direct singlet–singlet transfer) and, for both singlet–singlet and triplet–triplet EET, orbital overlap‐dependent interactions. The dominant orbital overlap‐dependent terms arise from through‐configuration interaction, which involves successive one‐electron transfers mediated via bridging ionic config...

Fluorescence lifetime measurements using a novel fiber‐optic laser scanning confocal microscope

The novel design of a fiber‐optic laser scanning confocal microscope is described. The optical fiber acts as a flexible light path for both the excitation and return beams and as the confocal pinhole of the microscope. The system is capable of imaging both reflective and fluorescent objects and offers considerable adaptability in use. With a mode‐locked dye laser excitation source, avalanche photodiode detector and time‐correlated photon counting electronics, spatially resolved fluorescence decay profiles from fluorescent dyes in solution and polymer films have been recorded.

RAFT synthesis of linear and star-shaped light harvesting polymers using di- and hexafunctional ruthenium polypyridine reagents

The syntheses of linear and star-shaped light harvesting polymers with well defined structure and narrow molecular weight distribution are described. These polymers have ruthenium polybipyridine moieties as the energy trap cores and styrene functionalized coumarin monomers as the light absorbing antenna chromophores. The polymers have been made by reversible addition–fragmentation chain transfer (RAFT) polymerisation using di- or hexafunctional ruthenium-containing RAFT agents. The resulting ruthenium-containing polymers have narrow molecular weight distribution (polydispersity < 1.1) and exhibit energy transfer efficiencies of up to 60% between the coumarin donor dyes and the ruthenium acceptor chromophores.

Long-lived photoinduced charge separation in a bridged C60-porphyrin dyad

Abstract Long-range photoinduced energy and electron transfer have been investigated in a novel dyad containing a zinc tetraarylporphyrin (PZn) donor and a C60 acceptor separated by a saturated norbornylogous bridge nine sigma bonds in length (PZn-9σ-C60). In non-polar solvents singlet-singlet energy transfer from PZn to C60 is observed but in benzonitrile efficient (> 90%) charge separation occurs with a rate constant of 1 × 1010 sec−1 to yield PZn.+-9σ-C60.−. The charge separated state exhibits a remarkably long lifetime for a dyad of 420 ns. This behaviour is discussed with reference to the energetics, dynamics and orbital symmetry properties of the states involved.

Excited state proton transfer in β-carboline

Abstract Steady state and time-resolved fluorescence techniques were used to investigate the excited state acid—base equilibria behaviour of β-carboline and 2-methyl-β-carboline in aqueous solutions. In acid conditions the β-carboline cation is responsible for light absorption and fluorescence (λmax = 450 nm; τF = 22.0 ns). However, in alkaline solutions excitation of the neutral species leads to the formation of the β-carboline cation by a rapid proton transfer with the solvent. A diffusion-controlled quenching of the excited state cation by OH− ions produces a zwitterion species which fluoresces with λmax at 510 nm (τF = 1.6 ns). The zwitterion is also formed after excitation of the ground state anion at pH 14. pK values for the ground state and excited state acid—base equilibria are reported.

Concentrating Aggregation-Induced Fluorescence in Planar Waveguides: A Proof-of-Principle

The photophysical properties of fluorescent dyes are key determinants in the performance of luminescent solar concentrators (LSCs). First-generation dyes – coumarin, perylenes, and rhodamines - used in LSCs suffer from both concentration quenching in the solid-state and small Stokes shifts which limit the current LSC efficiencies to below theoretical limits. Here we show that fluorophores that exhibit aggregation-induced emission (AIE) are promising materials for LSC applications. Experiments and Monte Carlo simulations show that the optical quantum efficiencies of LSCs with AIE fluorophores are at least comparable to those of LSCs with first-generation dyes as the active materials even without the use of any optical accessories to enhance the trapping efficiency of the LSCs. Our results demonstrate that AIE fluorophores can potentially solve some key limiting properties of first-generation LSC dyes.

Singlet oxygen quantum yields of potential porphyrin-based photosensitisers for photodynamic therapy

The singlet oxygen formation quantum yield (Phi(Delta)) for solutions of the di-cation, free-base and metallated forms of hematoporphyrin derivative (HpD), hematoporphyrin IX (Hp9) and a boronated protoporphyrin (BOPP) are reported using the method of direct detection of the characteristic phosphorescence following polychromatic excitation. Values of Phi(Delta) for the free-base form of all the porphyrins and the di-cation forms of Hp9 and HpD are in the range of 0.44 to 0.85 in the solvents investigated. Incorporation of zinc ions into the macrocycle reduces Phi(Delta) for all three porphyrins. BOPP facilitates the coordination of certain transition metals (Mn, Co and Cu) compared to Hp9 and HpD and results in a dramatic decrease in Phi(Delta). The experimental data suggest the introduction of low energy charge transfer states associated with the disruption of the planarity of the macrocyclic ring provides alternative non-radiative deactivation pathways. In BOPP, this non-planarity is augmented by the large closo-carborane peripheral substituent groups.