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Understanding hole/electron-transfer processes among interacting constituents of multicomponent molecular architectures is central to the fields of artificial photosynthesis and molecular electronics. One strategy for examining ground-state hole/electron transfer in oxidized tetrapyrrolic arrays entails analysis of the hyperfine interactions observed in the electron paramagnetic resonance (EPR) spectrum of the pi-cation radical. Herein, it is demonstrated that (203)Tl/(205)Tl hyperfine "clocks" are greatly superior to those provided by (1)H, (14)N, or (13)C owing to the fact that the (203)Tl/(205)Tl hyperfine couplings are much larger (15-25 G) than those of the (1)H, (14)N, or (13)C nuclei (1-6 G). The large (203)Tl/(205)Tl hyperfine interactions permit accurate simulations of the EPR spectra and the extraction of specific rates of hole/electron transfer. The (203)Tl/(205)Tl hyperfine clock strategy is applied to a series of seven porphyrin dyads. All of the dyads are joined at a meso position of the porphyrin macrocycle via linkers of a range of lengths and composition (diphenylethyne, diphenylbutadiyne, and (p-phenylene)(n), where n = 1-4); substituents such as mesityl at the nonlinking meso positions are employed to provide organic solubility. The hole/electron-transfer time constants are in the hundreds of picoseconds to sub-10 ns regime, depending on the specific porphyrin and/or linker. Density functional theory calculations on the constituents of the dyads are consistent with the view that the relative energies of the porphyrin versus linker highest occupied molecular orbitals strongly influence the hole/electron-transfer rates. Variable-temperature EPR studies further demonstrate that the hole/electron-transfer process is at best weakly activated (12-15 kJ mol(-1)) at room temperature and somewhat below. At lower temperatures, the process is essentially activationless. The weak activation is attributed to restricted torsional motions of the phenyl rings of the linker. Collectively, the studies provide the physical basis for the rational design of multicomponent architectures for efficient hole/electron transfer.

Photodynamic inactivation is a rapidly developing antimicrobial treatment that employs a nontoxic photoactivatable dye or photosensitizer in combination with harmless visible light to generate reactive oxygen species that are toxic to cells. Tetrapyrroles (e.g., porphyrins, chlorins, bacteriochlorins) are a class of photosensitizers that exhibit promising characteristics to serve as broad-spectrum antimicrobials. In order to bind to and efficiently penetrate into all classes of microbial cells, tetrapyrroles should have structures that contain (i) one or more cationic charge(s) or (ii) a basic group. In this report, we investigate the use of new stable synthetic bacteriochlorins that have a strong absorption band in the range 720 to 740 nm, which is in the near-infrared spectral region. Four bacteriochlorins with 2, 4, or 6 quaternized ammonium groups or 2 basic amine groups were compared for light-mediated killing against a gram-positive bacterium (Staphylococcus aureus), a gram-negative bacterium (Escherichia coli), and a dimorphic fungal yeast (Candida albicans). Selectivity was assessed by determining phototoxicity against human HeLa cancer cells under the same conditions. All four compounds were highly active (6 logs of killing at 1 microM or less) against S. aureus and showed selectivity for bacteria over human cells. Increasing the cationic charge increased activity against E. coli. Only the compound with basic groups was highly active against C. albicans. Supporting photochemical and theoretical characterization studies indicate that (i) the four bacteriochlorins have comparable photophysical features in homogeneous solution and (ii) the anticipated redox characteristics do not correlate with cell-killing ability. These results support the interpretation that the disparate biological activities observed stem from cellular binding and localization effects rather than intrinsic electronic properties. These findings further establish cationic bacteriochlorins as extremely active and selective near-infrared activated antimicrobial photosensitizers, and the results provide fundamental information on structure-activity relationships for antimicrobial photosensitizers.

Photodynamic therapy (PDT) is a rapidly developing approach to treating cancer that combines harmless visible and near-infrared light with a nontoxic photoactivatable dye, which upon encounter with molecular oxygen generates the reactive oxygen species that are toxic to cancer cells. Bacteriochlorins are tetrapyrrole compounds with two reduced pyrrole rings in the macrocycle. These molecules are characterized by strong absorption features from 700 to >800 nm, which enable deep penetration into tissue. This report describes testing of 12 new stable synthetic bacteriochlorins for PDT activity. The 12 compounds possess a variety of peripheral substituents and are very potent in killing cancer cells in vitro after illumination. Quantitative structure-activity relationships were derived, and subcellular localization was determined. The most active compounds have both low dark toxicity and high phototoxicity. This combination together with near-infrared absorption gives these bacteriochlorins great potential as photosensitizers for treatment of cancer.

Understanding electronic communication among interacting constituents of multicomponent molecular architectures is important for rational design in diverse fields including artificial photosynthesis and molecular electronics. One strategy for examining ground-state hole/electron transfer in an oxidized tetrapyrrolic array relies on analysis of the hyperfine interactions observed in the EPR spectrum of the pi-cation radical. This strategy has been previously employed to probe the hole/electron-transfer process in oxidized multiporphyrin arrays of normal isotopic composition, wherein (1)H and (14)N serve as the hyperfine "clocks", and in arrays containing site-specific (13)C-labels, which serve as additional hyperfine clocks. Herein, the hyperfine-clock strategy is applied to dyads of dihydroporphyrins (chlorins). Chlorins are more closely related structurally to chlorophylls than are porphyrins. A de novo synthetic strategy has been employed to introduce a (13)C label at the 19-position of the chlorin macrocycle, which is a site of large electron/hole density and is accessible synthetically beginning with (13)C-nitromethane. The resulting singly (13)C-labeled chlorin was coupled with an unlabeled chlorin to give a dyad wherein a diphenylethyne linker spans the 10-positions of the two zinc chlorins. EPR studies of the monocations of both the natural abundance and (13)C-labeled zinc chlorin dyads and benchmark zinc chlorin monomers reveal that the time scale for hole/electron transfer is in the 4-7 ns range, which is 5-10-fold longer than that in analogous porphyrin arrays. The slower hole/electron transfer rate observed for the chlorin versus porphyrin dyads is attributed to the fact that the HOMO is a(1u)-like for the chlorins versus a(2u)-like for the porphyrins; the a(1u)-like orbital exhibits little (or no) electron/hole density at the site of linker attachment whereas the a(2u)-like orbital exhibits significant electron/hole density at this site. Collectively, the studies of the chlorin and porphyrin dyads provide insights into the structural features that influence the hole/electron-transfer process.

The excited-state photodynamics of the neutral and one-electron-oxidized forms of five porphyrin dyads were studied in benzonitrile containing tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Each dyad contains a zinc porphyrin (Zn) and a free base porphyrin (Fb) joined by a linear biphenylene (Phi(2)), terphenylene (Phi(3)), quaterphenylene (Phi(4)), diphenylbutadiyne (L), or phenylethyne (E) linker (ZnFbPhi(2), ZnFbPhi(3), ZnFbPhi(4), ZnFbL, ZnFbE). The findings along with recent results on the neutral and oxidized forms of ZnFb dyads containing a diphenylethyne or phenylene linker (ZnFbU, ZnFbPhi) and steric hindrance to porphyrin-linker internal rotation at one or both ends of a diarylethyne linker (ZnFbD, ZnFbP, ZnFbB) give insights into the effects of linker characteristics (length, orbital energies, orbital overlap with the porphyrins) on the rate constants for excited-state energy transfer, excited-state hole transfer, and ground-state hole transfer. Analysis of the results is aided by density functional theory molecular orbital calculations and Forster energy-transfer calculations. Although the rate constants for linker-mediated through-bond excited-state energy transfer can be modulated significantly using a number of molecular design criteria (e.g., linker characteristics, interplay between porphyrin orbital characteristics, and linker attachment site), ground-state hole transfer, which also occurs via a linker-mediated through-bond electron-exchange mechanism, is primarily affected by the free-energy driving force for the process as dictated by the redox characteristics of the interacting porphyrins. The insights gained from this study should aid in the design of next-generation multichromophore arrays for solar energy applications.

The photophysical properties of two energy-transfer dyads that are potential candidates for near-infrared (NIR) imaging probes are investigated as a function of solvent polarity. The dyads (FbC-FbB and ZnC-FbB) contain either a free base (Fb) or zinc (Zn) chlorin (C) as the energy donor and a free base bacteriochlorin (B) as the energy acceptor. The dyads were studied in toluene, chlorobenzene, 1,2-dichlorobenzene, acetone, acetonitrile and dimethylsulfoxide (DMSO). In both dyads, energy transfer from the chlorin to bacteriochlorin occurs with a rate constant of approximately (5-10 ps)(-1) and a yield of >99% in nonpolar and polar media. In toluene, the fluorescence yields (Phif=0.19) and singlet excited-state lifetimes (tau approximately 5.5 ns) are comparable to those of the benchmark bacteriochlorin. The fluorescence yield and excited-state lifetime decrease as the solvent polarity increases, with quenching by intramolecular electron (or hole) transfer being greater for FbC-FbB than for ZnC-FbB in a given solvent. For example, the Phif and tau values for FbC-FbB in acetone are 0.055 and 1.5 ns and in DMSO are 0.019 and 0.28 ns, whereas those for ZnC-FbB in acetone are 0.12 and 4.5 ns and in DMSO are 0.072 and 2.4 ns. The difference in fluorescence properties of the two dyads in a given polar solvent is due to the relative energies of the lowest energy charge-transfer states, as assessed by ground-state redox potentials and supported by molecular-orbital energies derived from density functional theory calculations. Controlling the extent of excited-state quenching in polar media will allow the favorable photophysical properties of the chlorin-bacteriochlorin dyads to be exploited in vivo. These properties include very large Stokes shifts (85 nm for FbC-FbB, 110 nm for ZnC-FbB) between the red-region absorption of the chlorin and the NIR fluorescence of the bacteriochlorin (lambdaf=760 nm), long bacteriochlorin excited-state lifetime (approximately 5.5 ns), and narrow (

The mechanisms and dynamics of quenching of a photoexcited free base porphyrin (Fb*) covalently linked to a nearby oxidized zinc porphyrin (Zn(+)) have been investigated in a set of five dyads using time-resolved absorption spectroscopy. The dyads include porphyrins joined at the meso-positions by a diphenylethyne linker or a diarylethyne linker with 2,6-dimethyl substitution on either one or both of the aryl rings. Another dyad is linked at the beta-pyrrole positions of the porphyrins via a diphenylethyne linker. The type of linker and attachment site modulate the interporphyrin through-bond electronic coupling via steric hindrance (porphyrin-linker orbital overlap) and attachment motif (porphyrin electron density at the connection site). For each ZnFb dyad, the zinc porphyrin is selectively electrochemically oxidized (to produce Zn(+)Fb), the free base porphyrin is selectively excited with a 130 fs flash (to produce Zn(+)Fb*), and the subsequent dynamics monitored. The Zn(+)Fb* excited state has a lifetime of approximately 3 to approximately 30 ps (depending on the linker steric hindrance and attachment site) and decays by parallel excited-state energy- and hole-transfer pathways. The relative yields of the two channels depend on a number of factors including the linker-mediated through-bond electronic coupling and a modest (< or =20%) Forster through-space contribution for the energy-transfer route. One product of Zn(+)Fb* decay is the metastable ground-state ZnFb(+), which decays to the Zn(+)Fb preflash state by ground-state hole transfer with a linker-dependent rate constant of (20 ps)(-1) to (150 ps)(-1). Collectively, these results provide a detailed understanding of the mechanism and dynamics of quenching of excited porphyrins by nearby oxidized sites, as well as the dynamics of ground-state hole transfer between nonequivalent porphyrins (Zn and Fb). The findings also lay the foundation for the study of ground-state hole transfer between identical porphyrins (e.g., Zn/Zn, Fb/Fb) in larger multiporphyrin arrays wherein a hole is selectively placed via electrochemical oxidation.

Excited-state charge separation in molecular architectures has been widely explored, yet ground-state hole (or electron) transfer, particularly involving equivalent pigments, has been far less studied, and direct quantitation of the rate of transfer often has proved difficult. Prior studies of ground-state hole transfer between equivalent zinc porphyrins using electron paramagnetic resonance techniques give a lower limit of approximately (50 ns)(-1) on the rates. Related transient optical studies of hole transfer between inequivalent sites [zinc porphyrin (Zn) and free base porphyrin (Fb)] give an upper limit of approximately (20 ps)(-1). Thus, a substantial window remains for the unknown rates of ground-state hole transfer between equivalent sites. Herein, the ground-state hole-transfer processes are probed in a series of oxidized porphyrin triads (ZnZnFb) with the focus being on determination of the rates between the nominally equivalent sites (Zn/Zn). The strategy builds upon recent time-resolved optical studies of the photodynamics of dyads wherein a zinc porphyrin is electrochemically oxidized and the attached free base porphyrin is photoexcited. The resulting energy- and hole-transfer processes in the oxidized ZnFb dyads are typically complete within 100 ps of excitation. Such processes are also present in the triads and serve as a starting point for determining the rates of ground-state hole transfer between equivalent sites in the triads. The rate constant of the Zn/Zn hole transfer is found to be (0.8 ns)(-1) for diphenylethyne-linked zinc porphyrins and increases only slightly to (0.6 ns)(-1) when a shorter phenylene linker is utilized. The rate decreases slightly to (1.1 ns)(-1) when steric constraints are introduced in the diarylethyne linker. In general, the rate constants for ground-state Zn/Zn hole transfer in oxidized arrays are a factor of 40 slower than those for Zn/Fb transfer. Collectively, the findings should aid the design of next-generation molecular architectures for applications in solar-energy conversion.

Insight into the electronic communication between the individual constituents of multicomponent molecular architectures is essential for the rational design of molecular electronic and/or photonic devices. To clock the ground-state hole/electron-transfer process in oxidized multiporphyrin architectures, a p-diphenylethyne-linked zinc porphyrin dyad was prepared wherein one porphyrin bears two (13)C atoms and the other porphyrin is unlabeled. The (13)C atoms are located at the 1- and 9-positions (alpha-carbons symmetrically disposed to the position of linker attachment), which are sites of electron/spin density in the a(1u) HOMO of the porphyrin. The (13)C labels were introduced by reaction of KS(13)CN with allyl bromide to give the allyl isothiocyanate, which upon Trofimov pyrrole synthesis followed by methylation gave 2-(methylthio)pyrrole-2-(13)C. Reaction of the latter with paraformaldehyde followed by hydrodesulfurization gave dipyrromethane-1,9-(13)C, which upon condensation with a dipyrromethane-1,9-dicarbinol bearing three pentafluorophenyl groups gave the tris(pentafluorophenyl)porphyrin bearing (13)C labels at the 1,9-positions and an unsubstituted meso (5-) position. Zinc insertion, bromination at the 5-position, and Suzuki coupling with an unlabeled porphyrin bearing a suitably functionalized diphenylethyne linker gave the regiospecifically labeled zinc porphyrin dyad. Examination of the monocation of the isotopically labeled dyad via electron paramagnetic resonance (EPR) spectroscopy (and comparison with the monocations of benchmark monomers, where hole transfer cannot occur) showed that the hole transfer between porphyrin constituents of the dyad is slow (<10(6) s(-1)) on the EPR time scale at room temperature. The slow rate stems from the a(1u) HOMO of the electron-deficient porphyrins, which has a node at the site of linker connection. In contrast, analogous dyads of electron-rich porphyrins (wherein the HOMO is a(2u) and has a lobe at the site of linker connection) studied previously exhibit rates of hole transfer that are fast (>5 x 10(7) s(-1)) on the EPR time scale at room temperature.

Understanding energy transfer among hydroporphyrins is of fundamental interest and essential for a wide variety of photochemical applications. Toward this goal, a synthetic free base ethynylphenylchlorin has been coupled with a synthetic free base bromobacteriochlorin to give a phenylethyne-linked chlorin-bacteriochlorin dyad (FbC-pe-FbB). The chlorin and bacteriochlorin are each stable toward adventitious oxidation because of the presence of a geminal dimethyl group in each reduced pyrrole ring. A combination of static and transient optical spectroscopic studies indicate that excitation into the Qy band of the chlorin constituent (675 nm) of FbC-pe-FbB in toluene results in rapid energy transfer to the bacteriochlorin constituent with a rate of approximately (5 ps)(-1) and efficiency of >99%. The excited bacteriochlorin resulting from the energy-transfer process in FbC-pe-FbB has essentially the same fluorescence characteristics as an isolated monomeric reference compound, namely a narrow (12 nm fwhm) fluorescence emission band at 760 nm and a long-lived (5.4 ns) Qy excited state that exhibits a significant fluorescence quantum yield (Phif=0.19). Förster calculations are consistent with energy transfer in FbC-pe-FbB occurring predominantly by a through-space mechanism. The energy-transfer characteristics of FbC-pe-FbB are compared with those previously obtained for analogous phenylethyne-linked dyads consisting of two porphyrins or two oxochlorins. The comparisons among the sets of dyads are facilitated by density functional theory calculations that elucidate the molecular-orbital characteristics of the energy donor and acceptor constituents. The electron-density distributions in the frontier molecular orbitals provide insights into the through-bond electronic interactions that can also contribute to the energy-transfer process in the different types of dyads.

Understanding the effects of substituents on the spectra of chlorins is essential for a wide variety of applications. Recent developments in synthetic methodology have made possible systematic studies of the properties of the chlorin macrocycle as a function of diverse types and patterns of substituents. In this paper, the spectral, vibrational and excited-state decay characteristics are examined for a set of synthetic chlorins. The chlorins bear substituents at the 5,10,15 (meso) positions or the 3,13 (beta) positions (plus 10-mesityl in a series of compounds) and include 24 zinc chlorins, 18 free base (Fb) analogs and one Fb or zinc oxophorbine. The oxophorbine contains the keto-bearing isocyclic ring present in the natural photosynthetic pigments (e.g. chlorophyll a). The substituents cause no significant perturbation to the structure of the chlorin macrocycle, as evidenced by the vibrational properties investigated using resonance Raman spectroscopy. In contrast, the fluorescence properties are significantly altered due to the electronic effects of substituents. For example, the fluorescence wavelength maximum, quantum yield and lifetime for a zinc chlorin bearing 3,13-diacetyl and 10-mesityl groups (662 nm, 0.28, 6.0 ns) differ substantially from those of the parent unsubstituted chlorin (602 nm, 0.062, 1.7 ns). Each of these properties of the lowest singlet excited state can be progressively stepped between these two extremes by incorporating different substituents. These perturbations are associated with significant changes in the rate constants of the decay pathways of the lowest excited singlet state. In this regard, the zinc chlorins with the red-most fluorescence also have the greatest radiative decay rate constant and are expected to have the fastest nonradiative internal conversion to the ground state. Nonetheless, these complexes have the longest singlet excited-state lifetime. The Fb chlorins bearing the same substituents exhibit similar fluorescence properties. Such combinations of factors render the chlorins suitable for a range of applications that require tunable coverage of the solar spectrum, long-lived excited states and red-region fluorescence.

The optical absorption spectra and redox properties are presented for 24 synthetic zinc chlorins and 18 free base analogs bearing a variety of 3,13 (beta) and 5,10,15 (meso) substituents. Results are also given for a zinc and free base oxophorbine, which contain the keto-bearing isocyclic ring present in the natural photosynthetic pigments such as chlorophyll a. Density functional theory calculations were carried out to probe the effects of the types and positions of substituents on the characteristics (energies, electron distributions) of the frontier molecular orbitals. A general finding is that the 3,13 positions are more sensitive to the effects of auxochromes than the 5,10,15 positions. The auxochromes investigated (acetyl>ethynyl>vinyl>aryl) cause a significant redshift and intensification of the Qy band upon placement at the 3,13 positions, whereas groups at the 5,10,15 positions result in much smaller redshifts that are accompanied by a decrease in relative Qy intensity. In addition, the substituent-induced shifts in first oxidation and reduction potentials faithfully track the energies of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The calculations show that the LUMO is shifted more by substituents than the HOMO, which derives from the differences in the electron densities of the two orbitals at the substituent sites. The trends in the substituent-induced effects on the wavelengths and relative intensities of the major features (By, Bx, Qx, Qy) in the near-UV to near-IR absorption bands are well accounted for using Gouterman's four-orbital model, which incorporates the effects of the substituents on the HOMO-1 and LUMO+1 in addition to the HOMO and LUMO. Collectively, the results and analysis presented herein and in the companion paper provide insights into the effects of substituents on the optical absorption, redox and other photophysical properties of the chlorins. These insights form a framework that underpins the rational design of chlorins for applications encompassing photomedicine and solar-energy conversion.

Understanding electronic communication among interacting chromophores provides the foundation for a variety of applications. The ground-state electronic communication in diphenylethyne-linked zinc-porphyrin dyads has been investigated by a novel molecular design strategy that entails introduction of a 13C-atom (*) at specific sites of the porphyrins where there is substantial electron density in the relevant frontier (highest occupied) molecular orbital. The site of 13C substitution is at a meso-position, either the site of attachment of the linker (proximal, "P") or the site trans to the linker (distal, "D"). The substituents (R) at the non-linking meso-positions are mesityl, tridec-7-yl ("swallowtail"), or p-tolyl groups. Altogether five isotopically labeled porphyrin dyads have been prepared. The hole/electron-transfer properties of one-electron oxidized dyads have been examined by electron paramagnetic resonance (EPR) spectroscopy. The introduction of the meso-13C label provides a "clock" (via the hyperfine interactions) that allows investigation of a time scale for hole transfer that is 3-4 times shorter than that provided by the natural abundance 14N nuclei of the pyrrole nitrogen atoms. The EPR studies indicate that the hole transfer, which has been previously shown to be fast on the time scale of the 14N hyperfine clock ( approximately 220 ns), remains fast on the time scale of the 13C hyperfine clock ( approximately 50 ns).

Low-frequency (90-435 cm(-1)) NIR-excitation (875-900 nm) resonance Raman (RR) studies are reported for the H(M202)G cavity mutant of bacterial photosynthetic reaction centers (RCs) from Rb. sphaeroides that was first described by Goldsmith et al. [(1996) Biochemistry 35: 2421-2428]. In this mutant, the His residue that axially ligates the Mg ion of the M-side bacteriochlorophyll (BChl) of the special pair primary donor (P) is replaced by a non-ligating Gly residue. Regardless, the Mg ion of P(M) in the H(M202)G RCs remains pentacoordinates and is presumably ligated by a water molecule, although this axial ligand has not been definitively identified. The low-frequency RR studies of the H(M202)G RCs are accompanied by studies of RCs exchanged with D(2)O and incubated with imidazole (Im). The RR studies of the cavity mutant RCs reveal the following: (1) The structure of P(M) in the H(M202)G RCs is different from that of the wild-type, consistent with an altered BChl core. (2) A water ligand for P(M) in the H(M202)G RCs is generally consistent with the low-frequency RR spectra. The Mg-OH(2) stretching vibration is tentatively assigned to a band at 318 cm(-1), a frequency higher than that of the Mg-His stretch of the native pigment ( approximately approximately 235 cm(-1)). (3) The BChl core structure of P(M) in the cavity mutant is rendered similar (but not identical) to that of the wild-type when the adventitious water axial ligand is replaced by Im. (4) Exchange with D(2)O results in more global structural changes, likely involving the protein, which in turn affect the structure of the BChls in P. (5) Assignment of the low-frequency vibrational spectrum of P is generally more complex than originally suggested.

The incorporation of symmetrically branched tridecyl ("swallowtail") substituents at the meso positions of porphyrins results in highly soluble building blocks. Synthetic routes have been investigated to obtain porphyrin building blocks bearing 1-4 swallowtail groups. Porphyrin dyads have been synthesized in which the zinc or free base (Fb) porphyrins are joined by a 4,4'-diphenylethyne linker and bear swallowtail (or n-pentyl) groups at the nonlinking meso positions. The swallowtail-substituted Zn(2)- and ZnFb-dyads are readily soluble in common organic solvents. Static absorption and fluorescence spectra and electrochemical data show that the presence of the swallowtail groups slightly raises the energy level of the filled a(2u)(pi) HOMO. EPR studies of the pi-cation radicals of the swallowtail porphyrins indicate that the torsional angle between the proton on the alkyl carbon and p-orbital on the meso carbon of the porphyrin is different from that of a porphyrin bearing linear pentyl groups. Regardless, the swallowtail substituents do not significantly affect the photophysical properties of the porphyrins or the electronic interactions between the porphyrins in the dyads. In particular, time-resolved spectroscopic studies indicate that facile excited-state energy transfer occurs in the ZnFb dyad, and EPR studies of the monocation radical of the Zn(2)-dyad show that interporphyrin ground-state hole transfer is rapid.

The synthesis and characterization of various triads composed of a linear array of two zinc porphyrins joined via an intervening bis(dipyrrinato)metal(II) complex are reported. The preparation exploits the facile complexation of dipyrrins with divalent metal ions to give bis(dipyrrinato)metal(II) complexes [abbreviated (dp)(2)M]. Copper(II) and palladium(II) chelates of dipyrrins (available by oxidation of dipyrromethanes) were prepared in 50-80% yield. A one-flask synthesis of bis(dipyrrinato)zinc(II) complexes was developed by oxidation of a dipyrromethane with DDQ or p-chloranil in the presence of Zn(OAc)(2).2H(2)O in THF ( approximately 80% yield). Three routes were developed for preparing porphyrin-dipyrrins: (1). Suzuki coupling of a boronate-substituted zinc porphyrin (ZnP) and bis[5-(4-iodophenyl)dipyrrinato]Pd(II) to give the (ZnP-dp)(2)Pd triad (50% yield), followed by selective demetalation of the (dp)(2)Pd unit by treatment with 1,4-dithiothreitol under neutral conditions (71% yield); (2). oxidation of a porphyrin-dipyrromethane with p-chloranil in the presence of Zn(OAc)(2).2H(2)O followed by chromatography on silica gel (71% yield); and (3). condensation of a dipyrrin-dipyrromethane and a dipyrromethane-dicarbinol under InCl(3) catalysis followed by oxidation with DDQ (10-16% yield). Four triads of form (ZnP-dp)(2)Zn were prepared in 83-97% yield by treatment of a porphyrin-dipyrrin with Zn(OAc)(2).2H(2)O at room temperature. Free base dipyrrins typically absorb at 430-440 nm, while the bis(dipyrrinato)metal complexes absorb at 460-490 nm. The fluorescence spectra/yields and excited-state lifetimes of the (ZnP-dp)(2)Zn triad in toluene show (1). efficient energy transfer from the bis(dipyrrinato)zinc(II) chromophore to the zinc porphyrins (98.5% yield), and (2). little or no quenching of the resulting excited zinc porphyrin relative to the isolated chromophore. Taken together, these results indicate that bis(dipyrrinato)zinc(II) complexes can serve as self-assembling linkers that further function as secondary light-collection elements in porphyrin-based light-harvesting arrays.