Photochemical Bleaching of an Elaborate Artificial Light-Harvesting Antenna.

The target artificial light-harvesting antenna, comprising 21 discrete chromophores arranged in a logical order, undergoes photochemical bleaching when dispersed in a thin plastic film. The lowest-energy component, which has an absorption maximum at 660 nm, bleaches through first-order kinetics at a relatively fast rate. The other components bleach more slowly, in part, because their excited-state lifetimes are rendered relatively short by virtue of fast intramolecular electronic energy transfer to the terminal acceptor. Two of the dyes, these being close to the terminal acceptor but interconnected through a reversible energy-transfer step, bleach by way of an autocatalytic step. Loss of the terminal acceptor, thereby switching off the energy-transfer route, escalates the rate of bleaching of these ancillary dyes. The opposite terminal, formed by a series of eight pyrene-based chromophores, does not bleach to any significant degree. Confirmation of the various bleaching steps is obtained by examination of an antenna lacking the terminal acceptor, where the autocatalytic route does not exist and bleaching is very slow.

Exciplex emission from a boron dipyrromethene (Bodipy) dye equipped with a dicyanovinyl appendage.

The photophysical properties of a prototypic donor-acceptor dyad, featuring a conventional boron dipyrromethene (Bodipy) dye linked to a dicyanovinyl unit through a meso-phenylene ring, have been recorded in weakly polar solvents. The absorption spectrum remains unperturbed relative to that of the parent Bodipy dye but the fluorescence is extensively quenched. At room temperature, the emission spectrum comprises roughly equal contributions from the regular π, π* excited-singlet state and from an exciplex formed by partial charge transfer from Bodipy to the dicyanovinyl residue. This mixture moves progressively in favor of the locally excited π, π* state on cooling and the exciplex is no longer seen in frozen media; the overall emission quantum yield changes dramatically near the freezing point of the solvent. The exciplex, which has a lifetime of approximately 1 ns at room temperature, can also be seen by transient absorption spectroscopy, in which it decays to form the locally excited triplet state. Under applied pressure (P<170 MPa), formation of the exciplex is somewhat hindered by restricted rotation around the semirigid linkage and again the emission profile shifts in favor of the π, π* excited state. At higher pressure (170

Effect of pressure on the solubilization of a fluorescent merocyanine dye by a nonionic surfactant.

The target dye, which is a derivative of Merocyanine 540 bearing a naphthoxazole headgroup, persists as a monomer in ethanol solution but dimerizes in water under ambient conditions. Analysis of the absorption spectrum indicates that the dimer has an oblique geometry with the two molecules being held at an angle of ca. 55°. Applying high pressure to the system forces the two molecules into closer contact, resulting in a decreased partial molar volume of 3.1 cm(3). One molecule of the monomeric dye enters a neutral micelle formed from Triton X-100, where it is highly fluorescent and free of exciton coupling. The result of applied pressure on these latter systems depends on the concentration of surfactant. Above the critical micelle concentration (CMC), applied pressure has little effect other than to increase the viscosity inside the micelle. At very low surfactant concentration, applied pressure forces monomeric dye into the dimeric form, as observed in the absence of Triton X-100. It is notable, however, that the pressure effect on the dimerization constant is exaggerated in the presence of surfactant. At intermediate surfactant concentrations, applied pressure leads to a marked change in the CMC. In particular, applied pressure reduces the partial molar volume of the micelle by ca. 7.9 cm(3) and induces micelle formation at relatively low concentration of surfactant. For example, the CMC falls from ca. 250 µM at atmospheric pressure to only 50 µM at 460 MPa.

Intramolecular excimer formation for covalently linked boron dipyrromethene dyes.

Photophysical properties have been recorded for a small series of covalently linked, symmetrical dimers formed around boron dipyrromethene (Bodipy) dyes. Within the series, a control dimer is unable to adopt a cofacial arrangement because of steric factors, while a second dimer possesses sufficient internal flexibility to form the cofacial geometry but with little overlap of the Bodipy units. The other three members of the series take up a cofacial arrangement with varying bite angles between the planes of the two Bodipy units. Fluorescence quantum yields and excited-state lifetimes indicate differing extents of electronic interaction between the two Bodipy head-groups, but only the compound with the smallest bite angle exhibits excimer emission in solution under ambient conditions. Time-resolved fluorescence studies show dual-exponential decay kinetics in each case, while temperature-dependent emission studies reveal reversible coupling between monomer and lower-energy excimer states. The latter is weakly fluorescent, at best, and is seen clearly only for dimers having small bite angles. The application of high pressure to dilute solutions of these dimers promotes excimer formation in certain cases and leads to loss of monomer-like fluorescence. Under high pressure, excimer emission is more evident, and the overall results can be discussed in terms of subtle structural rearrangements that favor excimer formation.

Photophysical properties and singlet oxygen production by ruthenium(II) complexes of benzo[i]dipyrido[3,2-a:2',3'-c]phenazine: spectroscopic and TD-DFT study.

The photophysical properties of a series of Ru(II) complexes containing benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (dppn) as a ligand are reported. Transient absorption spectroscopy studies indicate that, in contrast to related Ru(dppz) complexes (dppz = dipyrido[3,2-a:2',3'-c]phenazine), the excited state of all the dppn systems is a long-lived pipi* triplet state. Computational studies (DFT and TD-DFT) confirm that the excited state is based on the dppn ligand. Near-infrared luminescence studies reveal that the complexes are efficient singlet oxygen sensitizers with yields of 70-83%.

Europium complexes with high total photoluminescence quantum yields in solution and in PMMA.

We have prepared complexes of formula [Eu(beta-diketonate)(3)(DPEPO)] and shown quantitative excited-state energy transfer from the ligands combined with efficient Ln luminescence leading to exceptionally-high total photoluminescence quantum yield of up to 80% in solution and in PMMA.

Exploring the limits of Förster theory for energy transfer at a separation of 20 A.

Cutting the corner: An excellent agreement has been obtained between experimental and computed coulombic coupling matrix elements for donor-spacer-acceptor systems, which consist of a boron dipyrromethane donor and acceptor in various stages of protonation. This correlation occurs in spite of reservations about the validity of Förster theory being applied to intramolecular electronic energy transfer (ET) over short (e.g., 20 A) distances (see picture).

Solid-state gas sensors developed from functional difluoroboradiazaindacene dyes.

This article describes the synthesis and characterization of several new difluoroboradiazaindacene (BODIPY) dyes functionalized at the central 8-position by a phenyliodo, phenylheptynoate or phenylheptynoic fragment and at the 3- or 3/5-position(s) by 4-dimethylaminophenylstyryl residue(s). Single-crystal structural determinations confirm the planarity of the dyes, while the absorption and fluorescence spectroscopic properties are highly sensitive to the state of protonation (or alkylation) of the terminal anilino donor group(s). Reversible color tuning from green to blue for absorption and from colorless (i.e., near-IR region) to red for fluorescence is obtained on successive addition of acid and base. The difunctionalized derivative is especially interesting in this respect and shows two well-resolved pK(a) values of 5.10 and 3.04 in acetonitrile. Addition of the first proton causes only small spectral changes and deactivates the molecule towards addition of the second proton. It is this latter step that accommodates the large change in absorption and emission properties, due to the reversible extinction of the intramolecular charge-transfer character inherent to this type of dye. The main focus of the work is the covalent anchoring of the dyes to inert, porous polyacrylate beads so as to form a solid-state sensor suitable for analysis of gases or flowing liquids. The final material is highly stable--its performance is undiminished after more than one year--and fully reversible over many cycles. The sensitivity is such that reactions can be followed by the naked eye and the detection limit is about 600 ppb for HCl and about 80 ppb for ammonia. Trace amounts of diphosgene can be detected, as can alkylating agents. The sensing action is indiscriminate and also operates when the beads are dispersed in aqueous media.

Excited state dynamics of a PtII diimine complex bearing a naphthalene-diimide electron acceptor.

A combination of picosecond time-resolved infrared spectroscopy, picosecond transient absorption spectroscopy, and nanosecond flash photolysis was used to elucidate the nature and dynamics of a manifold of the lowest excited states in Pt(phen-NDI)Cl 2 ( 1), where NDI = strongly electron accepting 1,4,5,8-naphthalene-diimide group. 1 is the first example of a Pt (II)-diimine-diimide dyad. UV/vis/IR spectroelectrochemistry and EPR studies of electrochemically generated anions confirmed that the lowest unoccupied molecular orbital (LUMO) in this system is localized on the NDI acceptor group. The lowest allowed electronic transition in Pt(phen-NDI)Cl 2 is charge-transfer-to-diimine of a largely Pt-->phen metal-to-ligand charge-transfer (MLCT) character. Excitation of 1 in the 355-395 nm range initiates a series of processes which involve excited states with the lifetimes of 0.9 ps ( (1)NDI*), 3 ps ( (3)MLCT), 19 ps (vibrational cooling of "hot" (3)NDI and of "hot" NDI ground state), and 520 mus ( (3)NDI). Excitation of 1 with 395 nm femtosecond laser pulses populates independently the (1)MLCT and the (1)NDI* excited states. A thermodynamically possible decay of the initially populated (1)MLCT to the charge-transfer-to-NDI excited state, [Pt (III)(phen-NDI (-*))Cl 2], is not observed. This finding could be explained by an ultrafast ISC of the (1)MLCT to the (3)MLCT state which lies about 0.4 eV lower in energy than [Pt (III)(phen-NDI (-*))Cl 2]. The predominant decay pathway of the (3)MLCT is a back electron transfer process with approximately 3 ps lifetime, which also causes partial population of the vibrationally hot ground state of the NDI fragment. The decay of the (1)NDI* state in 1 populates vibrationally hot ground state of the NDI, as well as vibrationally hot (3)NDI. The latter relaxes to form (3)NDI state, that is, [Pt(phen- (3)NDI)Cl 2]*, which possesses a remarkably long lifetime for a Pt (II) complex in fluid solution of 520 mus. The IR signature of this excited state includes the nu(CO) bands at 1607 and 1647 cm (-1), which are shifted considerably to lower energies if compared to their ground-state counterparts. The assignment of the vibrational bands is supported by the density-functional theory calculations in CH 2Cl 2. Pt(phen-NDI)Cl 2 acts as a modest photosensitizer of singlet oxygen.

Anthracene as a sensitiser for near-infrared luminescence in complexes of Nd(III), Er(III) and Yb(III): an unexpected sensitisation mechanism based on electron transfer.

The ligand L(1), which contains a chelating 2-(2-pyridyl)benzimidazole (PB) unit with a pendant anthacenyl group An connected via a methylene spacer, (L(1) = PB-An), was used to prepare the 8-coordinate lanthanide(III) complexes [Ln(hfac)(3)(L(1))] (Ln = Nd, Gd, Er, Yb) which have been structurally characterised and all have a square antiprismatic N(2)O(6) coordination geometry. Whereas free L(1) displays typical anthracene-based fluorescence, this fluorescence is completely quenched in its complexes. The An group in L(1) acts as an antenna unit: in the complexes [Ln(hfac)(3)(L(1))] (Ln = Nd, Er, Yb) selective excitation of the anthracene results in sensitised near-infrared luminescence from the lanthanide centres with concomitant quenching of An fluorescence. Surprisingly, the anthracene fluorescence is also quenched even in the Gd(III) complex and in its Zn(II) adduct in which quenching via energy transfer to the metal centre is not possible. It is proposed that the quenching of anthracene fluorescence in coordinated L(1) arises due to intra-ligand photoinduced electron-transfer from the excited anthracene chromophore (1)An* to the coordinated PB unit generating a short-lived charge-separated state [An(.+)-PB(.-)] which collapses by back electron-transfer to give (3)An*. This electron-transfer step is only possible upon coordination of L(1) to the metal centre, which strongly increases the electron acceptor capability of the PB unit, such that (1)An* --> PB PET is endoergonic in free L(1) but exergonic in its complexes. Thus, rather than a conventional set of steps ((1)An* -->(3)An* --> Ln), the sensitization mechanism now includes (1)An* --> PB photoinduced electron transfer to generate charge-separated [An(.+)-PB(.-)], then back electron-transfer to generate (3)An* which finally sensitises the Ln(III) centre via energy transfer. The presence of (3)An* in L(1) and its complexes is confirmed by nanosecond transient absorption studies, which have also shown that the (3)An* lifetime in the Nd(III) complex matches the rise time of Nd-centred near-infrared emission, confirming that the final step of the sequence is (3)An* --> Ln(III) energy-transfer.