Photophysical Properties and Electronic Structure of Hydroporphyrin Dyads Exhibiting Strong Through-Space and Through-Bond Electronic Interactions.

Electronic interactions between tetrapyrroles are utilized in natural photosynthetic systems to tune the light-harvesting and energy-/charge-transfer processes in these assemblies. Such interactions also can be employed to tailor the electronic properties of tetrapyrrolic dyads and larger arrays for use in materials science and biomedical research. Here, we have utilized static and time-resolved optical spectroscopy to characterize the optical absorption and emission properties of a set of chlorin and bacteriochlorin dyads with varying degrees of through-bond (TB) and through-space (TS) interactions between the constituent macrocycles.

Photoisomerization of Enediynyl Linker Leads to Slipped Cofacial Hydroporphyrin Dyads with Strong Through-Bond and Through-Space Electronic Interactions.

Photoisomerization of 3,4-di(methoxycarbonyl)-enediyne linker in hydroporphyrin (chlorin or bacteriochlorin) dyads leads to thermally stable cis isomers, where macrocycles adopt a slipped cofacial mutual geometry with an edge-to-edge distance of ∼3.6 Å (determined by density functional theory (DFT) calculations). Absorption spectra exhibit a significant splitting of the long-wavelength Q band, which indicates a strong electronic coupling with a strength of V = ∼477 cm that increases to 725 cm upon metalation of hydroporphyrins.

Activatable Near-Infrared Fluorescence Imaging Using PEGylated Bacteriochlorin-Based Chlorin and BODIPY-Dyads as Probes for Detecting Cancer.

Near infrared (NIR) fluorescent probes are attractive tools for biomedical in vivo imaging due to the relatively deeper tissue penetration and lower background autofluorescence. Activatable probes are turned on only after binding to their target, further improving target to background ratios. However, the number of available activatable NIR probes is limited.

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 (O) photosensitization, and electronic properties have been examined. Marked bathochromic shifts of the long-wavelength Q 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 bands, corresponding to the absorption of each dyad component.

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.

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.

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.

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.