Electron vs energy transfer in arrays featuring two Bodipy chromophores axially bound to a Sn(IV) porphyrin via a phenolate or benzoate bridge

In this report we describe the synthesis of multichromophore arrays consisting of two Bodipy units axially bound to a Sn(IV) porphyrin center either via a phenolate (3) or via a carboxylate (6) functionality. Absorption spectra and electrochemical studies show that the Bodipy and porphyrin chromophores interact weakly in the ground state. However, steady-state emission and excitation spectra at room temperature reveal that fluorescence from both the Bodipy and the porphyrin of 3 are strongly quenched suggesting that, in the excited state, energy and/or electron transfer might occur. Indeed, as transient absorption experiments show, selective excitation of Bodipy in 3 results in a rapid decay (τ ≈ 2 ps) of the Bodipy-based singlet excited state and a concomitant rise of a charge-separated state evolving from the porphyrin-based singlet excited state. In contrast, room-temperature emission studies on 6 show strong quenching of the Bodipy-based fluorescence leading to sensitized emission from the porphyrin moiety due to a transduction of the singlet excited state energy from Bodipy to the porphyrin. Emission experiments at 77 K in frozen toluene reveal that the room-temperature electron transfer pathway observed in 3 is suppressed. Instead, Bodipy excitation in 3 and 6 results in population of the first singlet excited state of the porphyrin chromophore. Subsequently, intersystem crossing leads to the porphyrin-based triplet excited state.     

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 1.6×10¹⁰ 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 1.7×10¹¹ and 1.9×10¹⁰ 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.     

A Panchromatic Supramolecular Fullerene‐Based Donor–Acceptor Assembly Derived from a Peripherally Substituted Bodipy–Zinc Phthalocyanine Dyad

A panchromatic 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene –zinc phthalocyanine conjugate (Bodipy–ZnPc) 1 was synthesized starting from phthalocyanine aldehyde 4 , via dipyrromethane 3 and dipyrromethene 2 . Conjugate 1 represents the first example in which a Bodipy unit is tethered to the peripheral position of a phthalocyanine core. Electrochemical and optical measurements provided evidence for strong electronic interactions between the Bodipy and ZnPc constituents in the ground state of 1 . When conjugate 1 is subjected to photoexcitation in the spectral region corresponding to the Bodipy absorption, the strong fluorescence characteristic of the latter subunit is effectively quenched (i.e., ≥97 %). Excitation spectral analysis confirmed that the photoexcited Bodipy and the tethered ZnPc subunits interact and that intraconjugate singlet energy transfer occurs with an efficiency of ca. 25 %. Treatment of conjugate 1 with N‐pyridylfulleropyrrolidine ( 8 ), an electron‐acceptor system containing a nitrogen ligand, gives rise to the novel electron donor–acceptor hybrid 1 ? 8 through ligation to the ZnPc center. Irradiation of the resulting supramolecular ensemble within the visible range leads to a charge‐separated Bodipy–ZnPc^.+–C₆₀^.? radical‐ion‐pair state, through a sequence of excited‐state and charge transfers, characterized by a remarkably long lifetime of 39.9 ns in toluene.     

Coordination-driven self assembly of a brilliantly fluorescent rhomboid cavitand composed of bodipy-dye subunits

The two sp(3) hybridized fluorine atoms of a Bodipy dye have been synthetically replaced with the linear donor ligand 4-ethynylpyridine (-C≡C-Py) to form a rigid and highly symmetrical 109.5° building block in which the fluorophore subunit is vertically aligned to the plane formed by the -C≡C-Py donors. Upon reaction of the above tecton with a 90° organoplatinum acceptor unit, an intensely fluorescent rhomboid cavitand was manifested in solution. In contrast to the vast majority of coordination-driven self-assembled chromophoric systems, the present one fully conserves the excellent photophysical properties of the parent Bodipy dye. These unique features of the present metallosupramolecular entity constitute a fascinating metal-to-ligand self-assembled prototype for building compact and intensely luminescent materials with host-guest capabilities.     

Effect on Charge Transfer and Charge Recombination by Insertion of a Naphthalene‐Based Bridge in Molecular Dyads Based on Borondipyrromethene (Bodipy)

The photophysical properties of two related dyads based on a N,N‐dimethylaniline donor coupled to a fully‐alkylated boron dipyrromethene (Bodipy) acceptor are described. In one dyad, BD1 , the donor unit is attached directly to the Bodipy group, whereas in the second dyad, BD2 , a naphthalene spacer separates the two units. Cyclic voltammograms recorded for the two dyads in deoxygenated MeCN containing a background electrolyte are consistent with the reversible one‐electron oxidation of the N,N‐dimethylaniline group and the reversible one‐electron reduction of the Bodipy nucleus. There is a reasonable driving force (ΔG_CT) for photoinduced charge transfer from the N,N‐dimethylaniline to the Bodipy segment in MeCN. The charge‐transfer state is formed for BD1 extremely fast (1.5 ps), but decays over 140 ps to partially restore the ground state. On the other hand, the charge‐transfer state for BD2 is formed more slowly, but it decays extremely rapidly. Charge recombination for both dyads leads to a partial triplet formation on the Bodipy group. The naphthalene spacer group is extremely efficient at promoting back electron transfer.     

Accessing the long-lived triplet excited states in bodipy-conjugated 2-(2-hydroxyphenyl) benzothiazole/benzoxazoles and applications as organic triplet photosensitizers for photooxidations

Bodipy derivatives containing excited state intramolecular proton transfer (ESIPT) chromophores 2-(2-hydroxyphenyl) benzothiazole and benzoxazole (HBT and HBO) subunits were prepared (7-10). The compounds show red-shifted UV-vis absorption (530-580 nm; ε up to 50000 M(-1) cm(-1)) and emission compared to both HBT/HBO and Bodipy. The new chromophores show small Stokes shift (45 nm) and high fluorescence quantum yields (Φ(F) up to 36%), which are in stark contrast to HBT and HBO (Stokes shift up to 180 nm and Φ(F) as low as 0.6%). On the basis of steady state and time-resolved absorption spectroscopy, as well as DFT/TDDFT calculations, we propose that 7-9 do not undergo ESIPT upon photoexcitation. Interestingly, nanosecond time-resolved transient absorption spectroscopy demonstrated that Bodipy-localized triplet excited states were populated for 7-10 upon photoexcitation; the lifetimes of the triplet excited states (τ(T)) are up to 195 μs. DFT calculations confirm the transient absorptions are due to the triplet state. Different from the previous report, we demonstrated that population of the triplet excited states is not the result of ESIPT. The compounds were used as organic triplet photosensitizers for photooxidation of 1,5-dihydroxylnaphthalene. One of the compounds is more efficient than the conventional [Ir(ppy)(2)(phen)][PF(6)] triplet photosensitizer. Our result will be useful for design of new Bodipy derivatives, ESIPT compounds, and organic triplet photosensitizers, as well as for applications of these compounds in photovoltaics, photocatalysis and luminescent materials, etc.     

Fluorescence-based adenylyl cyclase assay adaptable to high throughput screening

The second messenger cAMP has been implicated in numerous cellular processes such as glycogen metabolism, muscle contraction, learning and memory, and differentiation and development. Genetic evidence suggests that the enzyme that produces cAMP, adenylyl cyclase (AC), may be involved in pathogenesis in many of these cellular processes. In addition, these data suggest that membrane-bound ACs may be valuable targets for therapeutics to treat pathogenesis of these processes. The development of a robust real-time adenylyl cyclase assay that can be scalable to high-throughput screening could help in the development of novel therapeutics. Here we report a novel fluorescence-based cyclase assay using Bodipy FL GTPgammaS (BGTPgammaS). The fluorescence of the Bodipy moiety of BGTPgammaS was dramatically enhanced by incubation with the minimal catalytic core of wild-type-AC (wt-AC) and a mutant with decreased purine selectivity (mut-AC), in an AC activation-dependent manner. No increase in fluorescence was observed using Bodipy FL ATPgammaS (BATPgammaS) as substrate for either wt-AC or mut-AC. Using BGTPgammaS, forskolin, Gsalpha.GTPgammaS and the divalent cation Mn(2+) potently enhanced the rate of fluorescence increase in a concentration-dependent manner. The fluorescence enhancement of the Bodipy moiety was inhibited by known inhibitors of AC such as 2'deoxy,3'AMP and 2',5'-dideoxy-3'ATP. Furthermore, the fluorescence assay is adaptable to 96-well and 384-well multiplate format and is thus applicable to high throughput screening methodologies.     

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<P<550 MPa), the molecule undergoes reversible distortion that has a small effect on the yield of π, π* emission but severely quenches exciplex fluorescence. In the limiting case, this high‐pressure effect decreases the molar volume of the solute by approximately 25 cm³ and opens a new channel for nonradiative deactivation of the excited‐state manifold.     

Phenyliodine(III) bis(trifluoroacetate) (PIFA)-promoted synthesis of Bodipy dimers displaying unusual redox properties

Phenyliodine(III) bis(trifluoroacetate) (PIFA) in conjunction with a Lewis acid promotes C-C coupling of Bodipy monomers leading to mixtures of various oligomers. When a single position is blocked with an iodo or phenyl group, formation of the dimer is favored. These dimers display two successive oxidation and two reduction waves separated on average by 260 and 130 mV, respectively, corresponding to each Bodipy subunit.     

Synthesis and photophysical properties of borondipyrromethene dyes bearing aryl substituents at the boron center

Several borondipyrromethene (Bodipy) dyes bearing an aryl nucleus linked directly to the boron center have been prepared under mild conditions. The choice of Grignard or lithio organo-metallic reagents allows the isolation of B(F)(aryl) or B(aryl)2 derivatives; where aryl refers to phenyl, anisyl, naphthyl, or pyrenyl fragments. A single crystal, X-ray structure determination for the bis-anisyl compound shows that the sp3 hybridized boron center remains pseudo-tetrahedral and that the B-C bond distances are 1.615 and 1.636 A. All compounds are electrode active but replacement of the fluorine atoms by aryl fragments renders the Bodipy unit more easily oxidized by 100 mV in the B(F)(aryl) and 180 mV in the B(aryl)2 compounds whereas reduction is made more difficult by a comparable amount. Strong fluorescence is observed from the Bodipy fluorophore present in each of the new dyes, with the radiative rate constant being independent of the nature of the aryl substituent. The fluorescence quantum yields are solvent dependent and, at least in some cases (aryl = anisyl or pyrenyl), nonradiative decay from the first-excited singlet state is strongly activated. There is no indication, however, for population of a charge-transfer state, in which the aryl substituent acts as donor and the Bodipy fragment functions as acceptor, that is strongly coupled to the ground state. Instead, it is conjectured that nonradiative decay involves a conformational change driven by the solvophobic effect. Thus, the rate of nonradiative decay in any given solvent increases with increasing surface accessibility (or molar volume) of the aryl substituent. Intramolecular energy transfer from pyrene or naphthalene residues to Bodipy is quantitative.     

Star-shaped panchromatic absorbing dyes based on a triazatruxene platform with diketopyrrolopyrrole and boron dipyrromethene substituents

The engineering of photoactive arrays built from a flat, functionalized triazatruxene (TAT) platform is described. The primary synthetic strategy involved the step by step connection of one, two or three bis(thienyl)diketopyrrolopyrrole (DPP) modules. Subsequent bromination of the pendent thiophene ring was not selective and provided a mixture of regioisomers. However, selective grafting of boron dipyrromethene (Bodipy) units via Pd-catalysed cross couplings enabled the construction of TAT/DPP/Bodipy arrays. As well, direct coupling of two green F-Bodipy units to dibromoTAT provided a substrate suitable for reaction with hydroxyl-propargyl-substituted red Bodipy dyes to give ready access to O-Bodipy linked multichromophoric systems. All the new dyes displayed strong absorption in the near-UV and visible region of the solar spectra (400–750 nm), with intramolecular cascade energy transfer enabling photon concentration and fluorescence at approximately 740 nm.     

ROFRET: A Molecular‐Scale Fluorescent Probe Displaying Viscosity‐Enhanced Intramolecular Förster Energy Transfer

The fluorescent probe ROFRET contains a Bodipy molecular rotor connected through a short triazole‐based spacer to a fully alkylated Bodipy. Förster resonance energy transfer takes place from the rotor to the other Bodipy, and is enhanced to a limiting value as the viscosity of the solvent increases. Time‐resolved spectroscopy and steady‐state studies are consistent with both forward and reverse energy transfer, and delayed fluorescence.     

Relationship between the spectral properties of solutions of borofluoride complex of alkylated dipyrromethene and the physicochemical parameters of solvents

Spectral and photophysical characteristics of borofluoride complex of alkylated dipyrromethene (Bodipy) are determined by means of absorption and fluorescence electron spectroscopy in various organic solvents. Dependences of the spectral and photophysical characteristics of Bodipy solutions vs. the physico-chemical parameters of solvents are obtained by linear regression analysis and the contribution from each parameter to the property under study is determined. It is established that the negative solvatochromic effect is intrinsic for Bodipy. It is concluded that specific interactions contribute substantially to the properties of the chromophore, which are determined by the electron donor properties of the solvent.     

Novel near-infrared fluorescent liquid crystal: Bodipy bearing multiple alkyl chains with columnar mesophase

By the typical Knoevenagel condensation of Bodipy with aldehyde derivatives, two novel Bodipy derivatives 3 and 6 with symmetric three and six alkyl chains were designed and prepared. The Bodipy derivative 3 with three alkyl chains showed no mesophase but the Bodipy derivative 6 with six alkyl chains possessed the orderly hexagonal columnar mesophase at room temperature. Both samples 3 and 6 exhibited the near-infrared fluorescence with high fluorescence quantum yields and larger Stokes shifts than their Bodipy precursors. Sample 6 was the first near-infrared fluorescent columnar liquid crystal with Bodipy core. This research presented a good strategy on constructing the near-infrared columnar Bodipy liquid crystal.     

Ganglioside partitioning and aggregation in phase-separated monolayers characterized by bodipy GM1 monomer/dimer emission

The distribution of Bodipy GM1 in monolayers of binary and ternary lipid mixtures with coexisting fluid and ordered phases has been examined using a combination of atomic force microscopy and near-field scanning optical microscopy. Monolayers deposited at high (30 mN/m) and low (5 or 10 mN/m) surface pressures were examined and compared to those containing the same concentration of unlabeled ganglioside. Measurements of monomer and dimer Bodipy emission were used to distinguish aggregated from dilute ganglioside levels. For binary DPPC/DOPC monolayers, Bodipy GM1 is distributed throughout both the fluid and ordered phases at low surface pressures, and both labeled and unlabeled gangliosides result in a reduction in the size of ordered DPPC domains at 0.4% and the appearance of small aligned ganglioside-rich domains at 4%. In agreement with earlier studies, GM1 is heterogeneously distributed in small islands in the condensed DPPC domains at high surface pressure. By contrast, Bodipy GM1 causes the disappearance of large DPPC domains at 0.4% and the formation of a new GM1-rich phase at 4%. The addition of both gangliosides leads to a comparable loss of large ordered domains at low surface pressure and the appearance of a new GM1-rich phase at 30 mN/m for ternary lipid mixtures containing cholesterol. The results demonstrate the complexity of GM1 partitioning and illustrate the utility of complementary AFM and high spatial resolution two-color fluorescence experiments for understanding Bodipy GM1 aggregation and distribution.     

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.     

Promising fast energy transfer system via an easy synthesis: Bodipy-porphyrin dyads connected via a cyanuric chloride bridge, their synthesis, and electrochemical and photophysical investigations

The boron dipyrrin (Bodipy) chromophore was combined with either a free-base or a Zn porphyrin moiety (H(2)P and ZnP respectively), via an easy synthesis involving a cyanuric chloride bridging unit, yielding dyads Bodipy-H(2)P (4) and Bodipy-ZnP (5). The photophysical properties of Bodipy-H(2)P (4) and Bodipy-ZnP (5) were investigated by UV-Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. The comparison of the absorption spectra and cyclic voltammograms of dyads Bodipy-H(2)P (4) and Bodipy-ZnP (5) with those of their model compounds Bodipy, H(2)P, and ZnP shows that the spectroscopic and electrochemical properties of the constituent chromophores are essentially retained in the dyads indicating negligible interaction between them in the ground state. In addition, luminescence and transient absorption experiments show that excitation of the Bodipy unit in Bodipy-H(2)P (4) and Bodipy-ZnP (5) into its first singlet excited state results in rapid Bodipy to porphyrin energy transfer-k(4) = 2.9 × 10(10) s(-1) and k(5) = 2.2 × 10(10) s(-1) for Bodipy-H(2)P (4) and Bodipy-ZnP (5), respectively-generating the first porphyrin-based singlet excited state. The porphyrin-based singlet excited states give rise to fluorescence or undergo intersystem crossing to the corresponding triplet excited states. The title complexes could also be used as precursors for further substitution on the third chlorine atom on the cyanuric acid moiety.     

8-Hydroxyquinoline-substituted boron-dipyrromethene compounds: synthesis, structure, and OFF-ON-OFF type of pH-sensing properties

A series of four novel 8-hydroxyquinoline-substituted boron-dipyrromethene derivatives, namely 4,4-difluoro-8-(5-(8-hydroxyquinoline))-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene (1), 4,4-difluoro-8-(5-(8-hydroxyquinoline))-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (2), 4,4-difluoro-8-(5-azastyryl-(8-hydroxyquinoline))-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene (3), and 4,4-difluoro-8-(5-azastyryl-(8-hydroxyquinoline))-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (4), have been synthesized and characterized by a series of spectroscopic methods. The molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction analyses. The two methyl substituents attached at C-1 and C-7 positions of boron-dipyrromethene (Bodipy) in compound 2 was revealed to prevent the free rotation of the 8-hydroxyquinoline (8-HQ) moiety, resulting in an almost vertical 8-HQ-Bodipy configuration of this compound. This is obviously different from those for 1 with the dihedral angle between 8-hydroxyquinoline and Bodipy moieties of 65.44 and 66.79° due to the lack of methyl substituents in the latter compound. The intense fluorescence from the Bodipy subunit of these compounds was revealed to gradually get diminished along with either decreasing or increasing the pH value under acidic and basic conditions, respectively, in particular for 1, 2, and 4 because of the photoinduced intramolecular electron transfer from excited Bodipy moiety to 8-HQ unit and just an opposite process. This renders these compounds the first OFF-ON-OFF type of pH-dependent fluorescent sensors. Nevertheless, both the intrinsic fluorescence of these compounds and their fluorescent quenching properties along with the change in the pH value have been found to depend on the steric configuration as well as the linking group between 8-hydroxyquinoline and Bodipy moieties, revealing the effect of molecular structure on their fluorescence properties.     

Exciplex Formation and Excited State Deactivation of Difluoroborondipyrromethene (Bodipy) Dyads

Two series of geometrically‐related dyads are discussed based on the difluoroborondipyrromethene (Bodipy) unit, and incorporating covalently attached hydroquinone/quinone groups. These units are anchored directly, or via a phenylene spacer, to the Bodipy core at the meso position in one series ( BD‐MHQ , BD‐MQ , BD‐MPHQ , BD‐MPQ ), but for the second series the attachment site is the 2‐position ( BD‐SHQ , BD‐SQ , BD‐SPHQ , BD‐SPQ ). The compounds show various levels of fluorescence depending on the oxidation state of the appended group and the substitution pattern. In non‐polar solvents such as toluene, diethyl ether and dichlorobenzene, the S₁ state deactivation of the Bodipy unit in BD‐SPQ and BD‐MPQ is dominated by ^{1, 3}exciplex formation, which has not been reported for Bodipy derivatives so far. In the latter molecule, the decay of the exciplex is divided between population of the Bodipy triplet state (13 %–21 %) and ground state reformation. This partitioning is not seen for the side‐on substituted derivative, BD‐SPQ , and only ground state reformation is observed following decay of the exciplex. This difference in behavior is explained by the radical‐pair inter‐system‐crossing mechanism, which more effectively operates in BD‐MPQ because of the orthogonality of the donor‐acceptor units. In the more polar solvent CH₃CN all the quinone derivatives show fast formation of the charge‐separated state (k_CS) followed by slower charge recombination (k_CR). The ratio k_CS/k_CR≤80.     

Bodipy-ruthenium(II) tris-bipyridyl dyads for homogeneous photochemical oxidations

Two Bodipy-ruthenium(II) tris-bipyridyl dyads were synthesized for use as sensitizers in photochemical oxidation reactions of organic substrates. The synthetic strategy involved the use of a simple ‘click’ CuAAC reaction to link a Bodipy subunit with an organometallic ruthenium(II) tris-bipyridyl complex. The linking triazole bridge was used to minimize electronic coupling between the two subunits. The dyads showed improved performance on organic substrate photo-oxidation reactions compared to the control compound without the Bodipy moiety.