Photo-driven water oxidation performed by supramolecular photocatalysts made of Ru(II) photosensitizers and catalysts.

Two new supramolecular photocatalysts made of covalently linked Ru(II) polypyridine chromophore subunits ([Ru(bpy)3]2+-type species; bpy = 2,2'-bipyridine) and [RuL(pic)2] (L = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) water oxidation catalyst subunits have been prepared. The new species, 1 and 2, contain chromophore and catalyst subunits in the molecular ratios 1:1 and 1:2, respectively. The model chromophore species [Ru(bpy)2(L1)]2+ (RuP1; L1=4-[2-(4-pyridyl)-2-hydroxyethyl]-4-methyl-2,2'-bipyridine) and [Ru(bpy)2(L2)]2+ (RuP2; L2 = 4,4'-bis[2-(4-pyridyl)-2-hydroxyethyl]-2,2'-bipyridine) have also been prepared. The absorption spectra, oxidation behavior, and luminescent properties of 1 and 2 have been studied, and the results indicate that each subunit largely maintains its own properties in the supramolecular species. However, the luminescence of the chromophore subunits is significantly quenched in 1 and 2 in comparison with the luminescence of the respective model species. Both 1 and 2 exhibit catalytic water oxidation in the presence of cerium ammonium nitrate, exhibiting an I2M mechanism, with a better efficiency than the known catalyst [RuL(pic)2] under the same experimental conditions. Upon light irradiation, in the presence of persulfate as a sacrificial acceptor agent, 1 and 2 are more efficient photocatalysts than a system made of separated [Ru(bpy)3]2+ and [RuL(pic)2] species, highlighting the advantage of using multicomponent, supramolecular species with respect to isolated species. The O-O bond formation step is I2M, even in the photo-driven process. The photocatalytic process of 2 is more efficient than that of 1, with the turnover frequency reaching a value of 1.2 s-1. A possible reason could be an increased local concentration of catalytic subunits in the needed bimolecular assembly required for the I2M mechanism in 2 with respect to 1, a consequence of the presence of two catalytic subunits in each multicomponent species 2.

Self-assembled systems for artificial photosynthesis.

The last few decades have seen an impressive development in molecular-based artificial photosynthesis, thanks to the design of integrated light-harvesting antennae, charge separation systems, and catalysts for water oxidation or hydrogen production based on covalently linked subunits. However, in recent years, self-assembly and spontaneous aggregation of components emerged - sometimes also through serendipity - for the preparation of multicomponent systems aimed to perform the basic processes needed for artificial photosynthesis. Here we critically discuss some key articles that have recently shown the potential of self-assembly for artificial photosynthesis, ranging from self-assembly of antennae and charge separation systems to integrated antenna/catalyst assemblies, to planned co-localization of various components into restricted environments. It is evident that self-assembly can generate emerging properties with respect to the non-aggregated species, and such emerging properties can be quite convenient for designing efficient photocatalytic systems.

Photoinduced Water Oxidation in Chitosan Nanostructures Containing Covalently Linked RuII Chromophores and Encapsulated Iridium Oxide Nanoparticles.

The luminophore Ru(bpy)2 (dcbpy)2+ (bpy=2,2'-bipyridine; dcbpy=4,4'-dicarboxy-2,2'-bipyridine) is covalently linked to a chitosan polymer; crosslinking by tripolyphosphate produced Ru-decorated chitosan fibers (NS-RuCh), with a 20 : 1 ratio between chitosan repeating units and RuII chromophores. The properties of the RuII compound are unperturbed by the chitosan structure, with NS-RuCh exhibiting the typical metal-to-ligand charge-transfer (MLCT) absorption and emission bands of RuII complexes. When crosslinks are made in the presence of IrO2 nanoparticles, such species are encapsulated within the nanofibers, thus generating the IrO2 ⊂NS-RuCh system, in which both RuII photosensitizers and IrO2 water oxidation catalysts are within the nanofiber structures. NS-RuCh and IrO2 ⊂NS-RuCh have been characterized by dynamic light scattering, scanning electronic microscopy, and energy-dispersive X-ray analysis, which indicated a 2 : 1 ratio between RuII chromophores and IrO2 species. Photochemical water oxidation has been investigated by using IrO2 ⊂NS-RuCh as the chromophore/catalyst assembly and persulfate anions as the sacrificial species: photochemical water oxidation yields O2 with a quantum yield (Φ) of 0.21, definitely higher than the Φ obtained with a similar solution containing separated Ru(bpy)3 2+ and IrO2 nanoparticles (0.05) or with respect to that obtained when using NS-RuCh and "free" IrO2 nanoparticles (0.10). A fast hole-scavenging process (rate constant, 7×104  s-1 ) involving the oxidized photosensitizer and the IrO2 catalyst within the IrO2 ⊂NS-RuCh system is behind the improved photochemical quantum yield of IrO2 ⊂NS-RuCh.

Stimuli-Responsive Internally Ion-Paired Supramolecular Polymer Based on a Bis-pillar[5]arene Dicarboxylic Acid Monomer.

A novel bis-pillar[5]arene dicarboxylic acid self-assembles in the presence of 1,12-diaminododecane to yield overall neutral, internally ion-paired supramolecular polymers. Their aggregation, binding mode, and morphology can be tuned by external stimuli such as solvent polarity, concentration, and base treatment.

Designing expanded bipyridinium as redox and optical probes for DNA.

We report on the light-switch behaviour of two head-to-tail expanded bipyridinium species as a function of their interaction with calf thymus DNA and polynucleotides. In particular, both DNA and polynucleotides containing exclusively adenine or guanine moieties quench the luminescence of the fused expanded bipyridinium species. This behaviour has been rationalized demonstrating that a reductive photoinduced electron transfer process takes place involving both adenine or guanine moieties. The charge separated state so produced recombines in the tens of picoseconds. These results could help in designing new organic substrates for application in DNA probing technology and lab on chip-based sensing systems.

Early photophysical events of a ruthenium(ii) molecular dyad capable of performing photochemical water oxidation and of its model compounds.

The early photophysical events occurring in the dinuclear metal complex [(ttb-terpy)(I)Ru(µ-dntpz)Ru(bpy)2]3+ (2; ttb-terpy = 4,4',4''-tri-tert-butyl-terpy; bpy = 2,2'-bipyridine; dntpz = 2,5-di-(1,8-dinaphthyrid-2-yl)pyrazine) - a species containing the chromophoric {(bpy)2Ru(µ-dntpz)}2+ subunit and the catalytic {(I)(ttb-terpy)Ru(µ-dntpz)}+ unit, already reported to be able to perform photocatalytic water oxidation - have been studied by ultrafast pump-probe spectroscopy in acetonitrile solution. The model species [Ru(bpy)2(dntpz)]2+ (1), [(bpy)2Ru(µ-dntpz)Ru(bpy)2]4+ (3), and [(ttb-terpy)(I)Ru((µ-dntpz)Ru[(ttb-terpy)(I)]2+ (4) have also been studied. For completeness, the absorption spectra, redox behavior of 1-4 and the spectroelectrochemistry of the dinuclear species 2-4 have been investigated. The usual 3MLCT (metal-to-ligand charge transfer) decay, characterized by relatively long lifetimes on the ns timescale, takes place in 1 and 3, whose lowest-energy level involves a {(bpy)2Ru(dntpz)}2+ unit, whereas for 2 and 4, whose lowest-energy excited state involves a 3MLCT centered on the {(I)(ttb-terpy)Ru(µ-dntpz)}+ subunit, the excited-state lifetimes are on the ps timescale, possibly involving population of a low-lying 3MC (metal-centered) level. Compound 2 also exhibits a fast process, with a time constant of 170 fs, which is attributed to intercomponent energy transfer from the MLCT state centered in the {(bpy)2Ru(µ-dntpz)}2+ unit to the MLCT state involving the {(I)(ttb-terpy)Ru(µ-dntpz)}+ unit. Both the intercomponent energy transfer and the MLCT-to-MC activation process take place from non-equilibrated MLCT states.

Photo-Induced Assembly of a Luminescent Tetraruthenium Square.

Self-assembly is a powerful synthetic tool that has led to the development of one-, two- and three-dimensional architectures. From MOFs to molecular flasks, self-assembled materials have proven to be of great interest to the scientific community. Here we describe a strategy for the construction and de-construction of a supramolecular structure through unprecedented photo-induced assembly and dis-assembly. The combination of two approaches, a [n×1]-directional bonding strategy and a ligand photo-dissociation strategy, allows the photo-induced assembly of a polypyridyl RuII precursor into a discrete molecular square. Diffusion-ordered NMR spectroscopy confirmed the synthesis of a higher volume species, while the identity of the species was established by high-resolution mass spectrometry and single-crystal X-ray diffraction studies. The self-assembled square is not obtained by classical thermal techniques in similar conditions, but is obtained only by light-irradiation. The tetraruthenium square has an excited-state lifetime (135 ns), 40 times that of its mononuclear precursor and its luminescence quantum yield (1.0 %) is three orders of magnitude higher. These remarkable luminescence properties are closely related to the relatively rigid square structure of the tetraruthenium assembly, as suggested by slow radiationless decay and transient absorption spectroscopy. The results described herein are a rare example of photo-induced assembly and dis-assembly processes, and can open the way to a new avenue in supramolecular chemistry, leading to the preparation of structurally organized supermolecules by photochemical techniques.

Multichromophoric hybrid species made of perylene bisimide derivatives and Ru(ii) and Os(ii) polypyridine subunits.

Herein, the synthesis and the photophysical and redox properties of a new perylene bisimide (PBI) species (L), bearing two 1,10-phenanthroline (phen) ligands at the two imide positions of the PBI, and its dinuclear Ru(ii) and Os(ii) complexes, [(bpy)2Ru(µ-L)Ru(bpy)2](PF6)4 (Ru2; bpy = 2,2'-bipyridine) and [(Me2-bpy)2Os(µ-L)Os(Me2-bpy)2](PF6)4 (Os2; Me2-bpy = (4,4'-dimethyl)-2,2'-bipyridine), are reported. The absorption spectra of the compounds are dominated by the structured bands of the PBI subunit due to the lowest-energy spin-allowed π-π* transition. The spin-allowed MLCT transitions in Ru2 and Os2 are inferred by the absorption at 350-470 nm, where the PBI absorption is negligible. The absorption band extends towards the red region for Os2 due to the spin-forbidden MLCT transitions, intensified by the heavy osmium center. The reduction processes of the compounds are dominated by two successive mono-electronic PBI-based processes, which in the metal complexes are slightly shifted compared to the free ligand. On oxidation, both metal complexes undergo an apparent bi-electronic process (at 1.31 V vs. SCE for Ru2 and 0.77 V for Os2), attributed to the simultaneous one-electron oxidation of the two weakly-interacting metal centers. In Ru2 and Os2, the intense fluorescence of L subunit (λmax, 535 nm; τ, 4.3 ns; Φ, 0.91) is fully quenched, mainly by photoinduced electron transfer from the metal centers, on the ps timescale (time constant, 11 ps in Ru2 and 3 ps in Os2). Such photoinduced electron transfer leads to the formation of a charge-separated state, which directly decays to the ground state in about 70 ps in Os2, but produces the triplet π-π* state of the PBI subunit in 35 ps in Ru2. The results provide information on the excited-state processes of the hybrid species combining two dominant classes of chromophore/luminophore species, the PBI and the metal polypyridine complexes, and can be used for future design on new hybrid species with made-to-order properties.

Photoinduced Charge Separation in a Donor-Spacer-Acceptor Dyad with N-Annulated Perylene Donor and Methylviologen Acceptor.

The first donor-acceptor species in which a strongly emissive N-annulated perylene dye is connected to a methylviologen electron acceptor unit via its macrocyclic nitrogen atom, is prepared by a stepwise, modular procedure. The absorption spectra, redox behavior, spectroelectrochemistry and photophysical properties of this dyad and of its model species are investigated, also by pump-probe fs transient absorption spectroscopy. Photoinduced oxidative electron transfer from the excited state of the dyad, centered on the N-annulated perylene subunit, to the appended methyviologen electron acceptor takes place in a few ps. The charge-separated species recombines in 19 ps. Our results indicate that N-annulated perylene can be connected to functional units by taking advantage of the macrocyclic nitrogen, an option never used until now, without losing their properties, so opening the way to new designing approaches.

Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

A novel molecular dyad, 1, made of a dinuclear {[Re2(µ-X)2(CO)6(µ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

Photochemical synthesis, characterization, and electrochemical sensing properties of CD-AuNP nanohybrids.

Among the existing nanosystems used in electrochemical sensing, gold nanoparticles (AuNPs) have attracted considerable attention owing to their intriguing chemical and physical properties such as good electrical conductivity, high electrocatalytic activity, and high surface-to-volume ratio. However, despite these useful characteristics, there are some issues due to their instability in solution that can give rise to aggregation phenomena and the use of hazardous chemicals in the most common synthetic procedures. With an aim to find a solution to these issues, recently, we prepared and characterized carbon dots (CDs), from olive solid wastes, and employed them as reducing and capping agents in photo-activated AuNP synthesis, thus creating CD-Au nanohybrids. These nanomaterials appear extremely stable in aqueous solutions at room temperature, are contemporary, and have been obtained using CDs, which are exclusively based on non-toxic elements, with an additional advantage of being generated from an otherwise waste material. In this paper, the synthesis and characterization of CD-Au nanohybrids are described, and the electrochemical experiments for hydroquinone detection are discussed. The results indicate that CD-Au acts as an efficient material for sensing hydroquinone, matching a wide range of interests in science from industrial processes to environmental pollution.

Ultrafast energy transfer in triptycene-grafted Bodipy scaffoldings.

A series of new compounds in which various Bodipy dyes are grafted logically on triptycene rigid structures are synthesized and characterized, and their absorption spectra and photophysical properties are studied, also by pump-probe transient absorption spectroscopy. The studied compounds are: the mono-Bodipy species TA, TB, and TC (where A, B, and C identify different Bodipy subunits absorbing and emitting at different wavelengths), the multichromophore species TA3 , which bears three identical A subunits, and the three multichromophoric species TAB, TBC, and TABC, all of them containing at least two different types of Bodipy subunits. The triptycene moiety plays the role of a rigid scaffold, keeping the various dyes at predetermined distances and allowing for a three-dimensional structural arrangement of the multichromophoric species. The absorption spectra of the multichromophoric Bodipy species are essentially additive, indicating that negligible inter-chromophoric interaction takes place at the ground state. Luminescence properties and transient absorption spectroscopy indicate that a very fast (on the picosecond time scale) and efficient photoinduced energy transfer occurs in all the multi-Bodipy species, with the lower-energy Bodipy subunits of each multi-Bodipy compounds playing the role of an electronic energy collector. In TAB, an energy transfer from the A-type Bodipy subunit to the B-type one takes place with a rate constant of 1.6×10(10) s(-1), whereas in TBC an energy transfer from the B-type Bodipy subunit to the C-type subunit is bi-exponential, exhibiting rate constants of 1.7×10(11) and 1.9×10(10) s(-1); the possible presence of different conformers with different donor-acceptor distances in this bichromophoric species is proposed to cause the bi-exponential energy-transfer process. Interpretation of the intricate energy-transfer pathways occurring in TABC is made with the help of the processes identified in the bichromophoric compounds. In all cases, the measured energy-transfer rate constants agree with a Förster mechanism for the energy-transfer processes.

Metal-Catalyzed Hydride Transfer from Alcohols to Photoexcited Dipyridophenazine.

Dipyridophenazine (dppz) is known to react with alcohols upon photoexcitation into an n-π* transition at 378 nm to yield dihydrodipyridophenazine (dppzH2 ). This process occurs via H-atom abstraction from alcohols and subsequent disproportionation of the dppzH• radical species, to the final product. This reaction shows a primary kinetic isotope effect (KIE = 4.9) in methanol/perdeuteromethanol solvents, consistent with H-atom transfer processes. Addition of excess Zn(II) ions to the dppz solution not only accelerates the rate of photoreduction, but also lowers the KIE to 1.7, indicating a change in reaction mechanism. We postulate that the coordination of the alcoholic solvent to Zn(II) activates the alcohol α C-H bonds toward hydride transfer processes which would be consistent with the lowered KIE and faster overall reduction of the aromatic ligand. Interestingly, this appears to be an intramolecular process in which the Zn(II) is coordinated to both the dppz ligand and the reactive alcohol, as a sharp inflection in the overall rate increase is observed at a Zn:dppz ratio of 2:1. At this ratio, the dominant dppz species involves a Zn(II) bound to one dppz and several solvent molecules (methanol and water).

Physicochemical Characterization and Antibacterial Properties of Carbon Dots from Two Mediterranean Olive Solid Waste Cultivars.

Carbon nanomaterials have shown great potential in several fields, including biosensing, bioimaging, drug delivery, energy, catalysis, diagnostics, and nanomedicine. Recently, a new class of carbon nanomaterials, carbon dots (CDs), have attracted much attention due to their easy and inexpensive synthesis from a wide range of precursors and fascinating physical, chemical, and biological properties. In this work we have developed CDs derived from olive solid wastes of two Mediterranean regions, Puglia (CDs_P) and Calabria (CDs_C) and evaluated them in terms of their physicochemical properties and antibacterial activity against Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa). Results show the nanosystems have a quasi-spherical shape of 12-18 nm in size for CDs_P and 15-20 nm in size for CDs_C. UV-Vis characterization indicates a broad absorption band with two main peaks at about 270 nm and 300 nm, respectively, attributed to the π-π* and n-π* transitions of the CDs, respectively. Both samples show photoluminescence (PL) spectra excitation-dependent with a maximum at λem = 420 nm (λexc = 300 nm) for CDs_P and a red-shifted at λem = 445 nm (λexc = 300 nm) for CDs_C. Band gaps values of ≈ 1.48 eV for CDs_P and ≈ 1.53 eV for CDs_C are in agreement with semiconductor behaviour. ζ potential measures show very negative values for CDs_C compared to CDs_P (three times higher, -38 mV vs. -18 mV at pH = 7). The evaluation of the antibacterial properties highlights that both CDs have higher antibacterial activity towards Gram-positive than to Gram-negative bacteria. In addition, CDs_C exhibit bactericidal behaviour at concentrations of 360, 240, and 120 µg/mL, while lesser activity was found for CDs_P (bacterial cell reduction of only 30% at the highest concentration of 360 µg/mL). This finding was correlated to the higher surface charge of CDs_C compared to CDs_P. Further investigations are in progress to confirm this hypothesis and to gain insight on the antibacterial mechanism of both cultivars.

Synthesis and Photophysics Characterization of Boronic Styril and Distyryl BODIPYs for Water-Based Dye-Sensitized Solar Cells.

In this study, two boronic acid BODIPYs are obtained through a microwave-assisted Knoevenagel reaction. The aim is to use them for the first time as dyes in a photosensitized solar cell (DSSC) to mimic chlorophyll photosynthesis, harvesting solar light and converting it into electricity. The microwave-assisted Knoevenagel reaction is a straightforward approach to extending the molecular conjugation of the dye and is applied for the first time to synthesize BODIPY's boronic acid derivatives. These derivatives have proved to be very useful for covalent deposition on titania. This work studies the photo-physical and electrochemical properties. Moreover, the photovoltaic performances of these two new dyes as sensitizers for DSSC are discussed. Experimental data show that both dyes exhibit photosensitizing activities in acetonitrile and water. In particular, in all the experiments, distyryl BODIPY was more efficient than styryl BODIPY. In this study, demonstrating the use of a natural component as a water-based electrolyte for boronic BODIPY sensitizers, we open new possibilities for the development of water-based solar cells.

SARS-CoV-2 and omicron variant detection with a high selectivity, sensitivity, and low-cost silicon bio-nanosensor.

The recent SARS-CoV-2 pandemic has highlighted the urgent need for novel point-of-care devices to be promptly used for a rapid and reliable large screening analysis of several biomarkers like genetic sequences and antibodies. Currently, one of the main limitations of rapid tests is the high percentage of false negatives in the presence of variants and, in particular for the Omicron one. We demonstrate in this work the detection of SARS-CoV-2 and the Omicron variant with a cost-effective silicon nanosensor enabling high sensitivity, selectivity, and fast response. We have shown that a silicon (Si) nanowires (NW) platform detects both Sars-CoV-2 and its Omicron variant with a limit of detection (LoD) of four effective copies (cps), without any amplification of the genome, and with high selectivity. This ultrasensitive detection of 4 cps allows to obtain an extremely early diagnosis paving the way for efficient and widespread tracking. The sensor is made with industrially compatible techniques, which in perspective may allow easy and cost-effective industrialization.

Luminescence of meso-pyrimidinylcorroles: relationship with substitution pattern and heavy atom effects.

The luminescence properties of a series of corroles containing multiple meso-pyrimidinyl groups have been studied. In particular, nine corroles containing two pyrimidinyl moieties, four corroles containing three pyrimidinyl groups and one corrole carrying a single pyrimidinyl substituent have been investigated, and their properties have been compared with some model species. The results indicate that the energy of the emissive π-π* corrole-core-based state is not significantly perturbed by the various substituents, whereas the emission lifetimes and quantum yields depend on the number of appended meso-dichloropyrimidinyl substituents. In particular, both emission lifetime and quantum yield decrease with increasing the number of meso-dichloropyrimidinyl substituents, whereas pyrimidinyl substituents which do not carry further electron withdrawing groups such as the chlorine atoms do not affect the corrole emission properties. Two hypotheses are taken into consideration to rationalize the results: (i) the presence of meso-dichloropyrimidinyl substituents could introduce low-lying CT states which mix with the corrole π-π* emissive level, so reducing emission efficiency; (ii) the ortho,ortho'-chlorine groups of the meso-pyrimidinyl substituents, which lie in the proximity of the corrole macrocycle, can increase the intersystem crossing rate constant of the corrole-based fluorescent state via the heavy-atom effect. A comparison of the results of the studied corrole compounds with formerly investigated species and the linear dependence of the radiationless decay rate constants and emission quantum yields on the squared spin-orbit coupling constants, calculated considering the number of chlorine atoms in ortho-position of the corrole meso-substituents, suggest that hypothesis (ii) is most likely the valid one. These results are of particular interest for the design of (a) corrole compounds featuring highly efficient triplet formation and (b) multicomponent systems containing photo-active corrole subunits and pyrimidinyl spacers.

Fast transport of HCl across a hydrophobic layer over macroscopic distances by using a Pt(II) compound as the transporter: micro- and nanometric aggregates as effective transporters.

Bis-(diethyl-dithioxamidate)platinum(ii) is able to transport HCl from the donor aqueous phase to the receiving one over a mean distance of 12 cm in about 3 minutes across an organic membrane in the bulk, without stirring of the organic phase, i.e. at a rate far exceeding the unidirectional macroscopic diffusion coefficient. The way in which this surprising phenomenon can happen is linked to the behaviour of HCl which, because of dynamic interactions with [Pt(HEt2C2N2S2)2] (in which HCl is hosted as a tight ion pair [Pt(H2Et2C2N2S2)2][Cl]2) and chloroform molecules, gives rise to observable nanometric and micrometric domains, more dense than the surrounding bulk, whose formation and disaggregation processes accelerate the unidirectional macroscopic diffusion of HCl. Thermodynamic parameters obtained from the study of acid-base behaviour of the system Pt(ii) species/HCl/CHCl3 also agree with the proposed mechanism of HCl transport.

Designing multifunctional expanded pyridiniums: properties of branched and fused head-to-tail bipyridiniums.

The multifaceted potentialities of expanded pyridiniums (EPs), based on one pyridinium core bearing a 4-pyridyl or 4-pyridylium as the N-pyridinio group, are established at both experimental and theoretical levels. Two classes of head-to-tail (htt) EPs were designed, and their first representative elements were synthesized and fully characterized. The branched (B) family is made up of 2,6-diphenyl-4-aryl-1,4'-bipyridin-1-ium (or 1,1'-diium) species, denoted 1B and 2B for monocationic EPs (with aryl = phenyl and biphenyl, respectively) and 1B(Me) and 2B(Me) for related quaternarized dicationic species. The series of fused (F) analogues comprises 9-aryl-benzo[c]benzo[1,2]quinolizino[3,4,5,6-ija][1,6]naphthyridin-15-ium species, denoted 1F and 2F, and their 2,15-diium derivatives referred to as 1F(Me) and 2F(Me). Electrochemistry (in MeCN vs SCE) reveals that branched EPs undergo a single reversible bielectronic reduction at ca. -0.92 V for 1B/2B and -0.59 V for 1B(Me)/2B(Me), whereas pericondensed species show two reversible monoelectronic reductions at ca. -0.83 and -1.59 V for 1F/2F and ca. -0.42 and -1.07 V for 1F(Me)/2F(Me). Regarding electronic absorption features, all htt-EP chromophores show absorptivity in the range of ca. 1-4 × 10(4) M(-1) cm(-1), with red-edge absorptions extending toward 450 and 500 nm (in MeCN) for 2B(Me) and 2F(Me), respectively. These lowest-energy pi-pi* transitions are ascribed to intramolecular charge transfer between the electron-releasing biphenyl group and the htt-bipyridinium electron-withdrawing subsystems. EPs display room-temperature photoemission quantum yields ranging from 10% to 50%, with the exception of 1B, and branched luminophores are characterized by larger Stokes shifts (8000-10 000 cm(-1)) than fused ones. Lastly, a method to predict the efficiency of photobiscyclization of branched EPs into fused ones, based on the analysis of computed difference maps in total electron density for singlet excited states, is proposed.

Vectorial photoinduced energy transfer between boron-dipyrromethene (Bodipy) chromophores across a fluorene bridge.

A series of novel multichromophoric, luminescent compounds has been prepared, and their absorption spectra, luminescence properties (both at 77 K in rigid matrix and at 298 K in fluid solution), and photoinduced intercomponent energy-transfer processes have been studied. The series contains two new multichromophoric systems 1 and 2, each one containing two different boron-dipyrromethene (Bodipy) subunits and one bridging fluorene species, and two fluorene-Bodipy bichromophoric species, 6 and 7. Three monochromophoric compounds, 3, 4, and 5, used as precursors in the synthetic process, were also fully characterized. The absorption spectra of the multichromophoric compounds are roughly the summation of the absorption spectra of their individual components, thus demonstrating the supramolecular nature of the assemblies. Luminescence studies show that quantitative energy transfer occurs in 6 and 7 from the fluorene chromophore to the Bodipy dyes. Luminescence studies, complemented by transient-absorption spectroscopy studies, also indicate that efficient inter-Bodipy energy transfer across the rigid fluorene spacer takes place in 1 and 2, with rate constants, evaluated by several experimental methods, between 2.0 and 7.0 x 10(9) s(-1). Such an inter-Bodipy energy transfer appears to be governed by the Förster mechanism. By taking advantage of the presence of various protonable sites in the substituents of the lower-energy Bodipy subunit of 1 and 2, the effect of protonation on the energy-transfer rates has also been investigated. The results suggest that control of energy-transfer rate and efficiency of inter-Bodipy energy transfer in this type of systems can be achieved by an external, reversible input.