BODIPY–Bacteriochlorin Energy Transfer Arrays: Toward Near-IR Emitters with Broadly Tunable, Multiple Absorption Bands

A series of energy transfer arrays, comprising a near-IR absorbing and emitting bacteriochlorin, and BODIPY derivatives with different absorption bands in the visible region (503–668 nm) have been synthesized. Absorption band of BODIPY was tuned by installation of 0, 1, or 2 styryl substituents [2-(2,4,6-trimethoxyphenyl)­ethenyl], which leads to derivatives with absorption maxima at 503, 587, and 668 nm, respectively. Efficient energy transfer (>0.90) is observed for each dyad, which is manifested by nearly exclusive emission from bacteriochlorin moiety upon BODIPY excitation. Fluorescence quantum yield of each dyad in nonpolar solvent (toluene) is comparable with that observed for corresponding bacteriochlorin monomer, and is significantly reduced in solvent of high dielectric constants (DMF), most likely by photoinduced electron transfer. Given the availability of diverse BODIPY derivatives, with absorption between 500–700 nm, BODIPY–bacteriochlorin arrays should allow for construction of near-IR emitting agents with multiple and broadly tunable absorption bands. Solvent-dielectric constant dependence of Φ_f in dyads gives an opportunity to construct environmentally sensitive fluorophores and probes

Symmetrical and Nonsymmetrical Meso–Meso Directly Linked Hydroporphyrin Dyads: Synthesis and Photochemical Properties

A series of a rigid meso–meso directly linked chlorin–chlorin, chlorin–bacteriochlorin, and bacteriochlorin–bacteriochlorin dyads, including free bases as well as Zn­(II), Pd­(II), and Cu­(II) complexes, has been synthesized, and their absorption, emission, singlet oxygen (¹O₂) photosensitization, and electronic properties have been examined. Marked bathochromic shifts of the long-wavelength Q_<i>y</i> absorption band and increase in fluorescence quantum yields in dyads, in comparison to the corresponding monomers, are observed. Nonsymmetrical dyads (except bacteriochlorin–bacteriochlorin) show two distinctive Q_<i>y</i> bands, corresponding to the absorption of each dyad component. A nearly quantitative S₁–S₁ energy transfer between hydroporphyrins in dyads, leading to an almost exclusive emission of hydroporphyrin with a lower S₁ energy, has been determined. Several symmetrical and all nonsymmetrical dyads exhibit a significant reduction in fluorescence quantum yields in solvents of high dielectric constants; this is attributed to the photoinduced electron transfer. The complexation of one macrocycle by Cu­(II) or Pd­(II) enhances intersystem crossing in the adjacent, free base dyad component, which is manifested by a significant reduction in fluorescence and increase in quantum yield of ¹O₂ photosensitization

Deep-Red Emissive BODIPY–Chlorin Arrays Excitable with Green and Red Wavelengths

We report here the synthesis and characterization of BODIPY–chlorin arrays containing a chlorin subunit, with tunable deep-red (641–685 nm) emission, and one or two BODIPY moieties, absorbing at 504 nm. Two types of arrays were examined: one where BODIPY moieties are attached through a phenylacetylene linker at the 13- or 3,13-positions of chlorin, and a second type where BODIPY is attached at the 10-position of chlorin through an amide linker. Each of the examined arrays exhibits an efficient (≥0.80) energy transfer from BODIPY to the chlorin moiety in both toluene and DMF and exhibits intense fluorescence of chlorin upon excitation of BODIPY at ∼500 nm. Therefore, the effective Stokes shift in such arrays is in the range of 140–180 nm. Dyads with BODIPY attached at the 10-position of chlorin exhibit a bright fluorescence in a range of solvents with different polarities (i.e., toluene, MeOH, DMF, and DMSO). In contrast to this, some of the arrays in which BODIPY is attached at the 3- or at both 3,13-positons of chlorin exhibit significant reduction of fluorescence in polar solvents. Overall, dyads where BODIPY is attached at the 10-position of chlorin exhibit ∼5-fold brighter fluorescence than corresponding chlorin monomers, upon excitation at 500 nm

Bacteriochlorin Dyads as Solvent Polarity Dependent Near-Infrared Fluorophores and Reactive Oxygen Species Photosensitizers

Symmetrical, near-infrared absorbing bacteriochlorin dyads exhibit gradual reduction of their fluorescence (intensity and lifetime) and reactive oxygen species photosensitization efficiency (ROS) with increasing solvent dielectric constant ε. For the directly linked dyad, significant reduction is observed even in solvents of moderate ε, while for the dyad containing a 1,4-phenylene linker, reduction is more parallel to an increase in solvent ε. Bacteriochlorin dyads are promising candidates for development of environmentally responsive fluorophores and ROS sensitizers

Amphiphilic BODIPY-Hydroporphyrin Energy Transfer Arrays with Broadly Tunable Absorption and Deep Red/Near-Infrared Emission in Aqueous Micelles

BODIPY-hydroporphyrin energy transfer arrays allow for development of a family of fluorophores featuring a common excitation band at 500 nm, tunable excitation band in the deep red/near-infrared window, and tunable emission. Their biomedical applications are contingent upon retaining their optical properties in an aqueous environment. Amphiphilic arrays containing PEG-substituted BODIPY and chlorins or bacteriochlorins were prepared and their optical and fluorescence properties were determined in organic solvents and aqueous surfactants. The first series of arrays contains BODIPYs with PEG substituents attached to the boron, whereas in the second series, PEG substituents are attached to the aryl at the <i>meso</i> positions of BODIPY. For both series of arrays, excitation of BODIPY at 500 nm results in efficient energy transfer to and bright emission of hydroporphyrin in the deep-red (640–660 nm) or near-infrared (740–760 nm) spectral windows. In aqueous solution of nonionic surfactants (Triton X-100 and Tween 20) arrays from the second series exhibit significant quenching of fluorescence, whereas properties of arrays from the first series are comparable to those observed in polar organic solvents. Reported arrays possess large effective Stokes shift (115–260 nm), multiple excitation wavelengths, and narrow, tunable deep-red/near-IR fluorescence in aqueous surfactants, and are promising candidates for a variety of biomedical-related applications