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 meso 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.

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 Φf in dyads gives an opportunity to construct environmentally sensitive fluorophores and probes.

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.

Achieving tunable, intense near-infrared absorption in molecular architectures with properties suitable for solar light harvesting and biomedical studies is of fundamental interest. Herein, we report the photophysical, redox, and molecular-orbital characteristics of nine hydroporphyrin dyads and associated benchmark monomers that have been designed and synthesized to attain enhanced light harvesting. Each dyad contains two identical hydroporphyrins (chlorin or bacteriochlorin) connected by a linker (ethynyl or butadiynyl) at the macrocycle β-pyrrole (3- or 13-) or meso (15-) positions. The strong electronic communication between constituent chromophores is indicated by the doubling of prominent absorption features, split redox waves, and paired linear combinations of frontier molecular orbitals. Relative to the benchmarks, the chlorin dyads in toluene show substantial bathochromic shifts of the long-wavelength absorption band (17–31 nm), modestly reduced singlet excited-state lifetimes (τS = 3.6–6.2 ns vs 8.8–12.3 ns), and increased fluorescence quantum yields (Φf = 0.37–0.57 vs 0.34–0.39). The bacteriochlorin dyads in toluene show significant bathochromic shifts (25–57 nm) and modestly reduced τS (1.6–3.4 ns vs 3.5–5.3 ns) and Φf (0.09–0.19 vs 0.17–0.21) values. The τS and Φf values for the bacteriochlorin dyads are reduced substantially (up to ∼20-fold) in benzonitrile. The quenching is due primarily to the increased S1 → S0 internal conversion that is likely induced by increased contribution of charge-resonance configurations to the S1 excited state in the polar medium. The fundamental insights gained into the physicochemical properties of the strongly coupled hydroporphyrin dyads may aid their utilization in solar-energy conversion and photomedicine.

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.

We report the synthesis and basic photophysical characterization of strongly conjugated hydroporphyrin (chlorin and bacteriochlorin) dyads. Hydroporphyrins are connected at their respective 13 (β) or 15 (meso) positions by ethynyl or butadiynyl linkers. Synthesis entails a series of palladium-catalyzed reactions, starting from appropriate bromobacteriochlorin or bromochlorin. Strong conjugation in the dyads results in a significant bathochromic shift of longest-wavelength (Qy-like) band, which in case of the 13–13′ ethynyl-linked bacteriochlorin dyad is positioned past 800 nm. The Qy-like band is broad and split for the 13–13′ linked chlorin and bacteriochlorin dyads. All dyads exhibit an intense, relatively narrow fluorescence emission band in nonpolar solvents. Bacteriochlorin dyads exhibit a strong dependence of fluorescence intensity on the solvent polarity, which results in more than 10-fold quenching of fluorescence in dimethylformamide. The assembling of hydroporphyrins into strongly conjugated arrays represents an efficient means to tune and expand their optical and photochemical properties, which should greatly broaden the properties attainable for these chromophores.

Design, synthesis, and optical properties of a series of novel chlorin–bacteriochlorin energy transfer dyads are described. Each dyad is composed of a common red-absorbing (645–646 nm) chlorin, as an energy donor, and a different near-IR emitting bacteriochlorin, as an energy acceptor. Each bacteriochlorin acceptor is equipped with a different set of auxochromes, so that each of them emits at a different wavelength. Dyads exhibit an efficient energy transfer (≥0.77) even for chlorin–bacteriochlorin pairs with large (up to 122 nm) separation between donor emission and acceptor absorption. Excitation of the chlorin donor results in relatively strong emission of the bacteriochlorin acceptor, with a quantum yield Φf range of 0.155–0.23 in toluene and 0.12–0.185 in DMF. The narrow, tunable emission band of bacteriochlorins enables the selection of a series of three dyads with well-resolved emissions at 732, 760, and 788 nm, and common excitation at 645 nm. Selected dyads have been also converted into bioconjugatable N-succinamide ester derivatives. The optical properties of the described dyads make them promising candidates for development of a family of near-IR fluorophores for simultaneous imaging of multiple targets, where the whole set of fluorophores can be excited with the common wavelength, and fluorescence from each can be independently detected.

Nonsymmetrical, multifunctional bacteriochlorin derivatives possessing different substituents at the β-pyrrolic positions have been prepared by stepwise, selective functionalization of 3,13-dibromo-5-methoxybacteriochlorin via palladium-coupling reactions. The new derivatives reported here include monovalent bioconjugatable bacteriochlorin, orthogonally protected bacteriochlorin amino acid, and push–pull bacteriochlorins. Taken together, this study provides a route to previously unavailable bacteriochlorin architectures for fundamental studies and diverse applications.