Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator.

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light.

Optoelectronic tuning of organoborylazadipyrromethenes via effective electronegativity at the metalloid center.

Organoborylazadipyrromethenes were synthesized from free base and fluoroborylazadipyrromethenes and characterized with regard to their structural and electronic properties. B-N bond lengths, along with photophysical and redox behavior, appear dependent on the effective electronegativity at the boron atom as tuned by its substituents, with stronger electronegativity correlating to a shorter B-N bond length, red-shifted absorbance, enhanced fluorescence lifetime and yield, and positively shifted redox potentials.

Imidazolium salts with varying anions as charge carriers for detection of neutral bis(triphenylphosphine)palladium(II) dichloride in electrospray ionization mass spectrometry.

RATIONALE: While electrospray ionization is a popular technique for mass analysis, without a charged species it is ineffective. This coupled with solvent restrictions hinders the analysis of organometallic complexes. Detecting neutral species whose solubility is limited to nonconventional solvents is a problem that can be overcome with the right charge carrier, which is described in this study. METHODS: Ionic liquids were synthesized and analyzed by electrospray ionization quadrupole ion trap mass spectrometry. The neutral palladium complex was also analyzed using different imidazolium salts as the charge carrier with the same method and instrumentation. Theoretical complements were also performed using Gaussian 09 at the density functional theory levels, using B3LYP functionals and the 6-31 g (d,p) basis set for geometry optimizations. RESULTS: Low concentration imidazolium salts in methanol showed aggregation behavior of the ionic liquid, where the cation peak and [cation](n+1)[anion]n peaks were observed in positive mode, while the [cation]n[anion](n+1) peaks were seen in negative mode. The unbound anion was observed in all the negative mode spectra except for the salt with the SCN anion when in THF. Solutions of PdCl2(PPh3)2 and a small amount of ionic liquid in THF showed the palladium complex adducted with the imidazolium cation for each of the ionic liquids studied. CONCLUSIONS: A charge carrier for a neutral organometallic complex was found in imidazolium salts, where the cation was observed as the ionizing agent. Differing ion intensities of the complex-adduct peak resulted from the anions ability to dissociate from the cation.

Visible light water splitting using dye-sensitized oxide semiconductors.

Researchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO(2) to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts. Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process. This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy)(3)](2+) derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA(2-)) or non-sacrificial donors (I(-)). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO(2).nH(2)O nanoparticles, a dye-sensitized TiO(2) electrode becomes the photoanode of a water-splitting photoelectrochemical cell. Although this system is an interesting proof-of-concept, the performance of these cells is still poor (approximately 1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain.

Photoassisted overall water splitting in a visible light-absorbing dye-sensitized photoelectrochemical cell.

Iridium oxide nanoparticles stabilized by a heteroleptic ruthenium tris(bipyridyl) dye were used as sensitizers in photoelectrochemical cells consisting of a nanocrystalline anatase anode and a Pt cathode. The dye coordinated the IrO(2) x nH(2)O nanoparticles through a malonate group and the porous TiO(2) electrode through phosphonate groups. Under visible illumination (lambda > 410 nm) in pH 5.75 aqueous buffer, oxygen was generated at anode potentials positive of -325 mV vs Ag/AgCl and hydrogen was generated at the cathode. The internal quantum yield for photocurrent generation was ca. 0.9%. Steady-state luminescence and time-resolved flash photolysis/transient absorbance experiments were done to measure the rates of forward and back electron transfer. The low quantum yield for overall water splitting in this system can be attributed to slow electron transfer (approximately 2.2 ms) from IrO(2) x nH(2)O to the oxidized dye. Forward electron transfer does not compete effectively with the back electron transfer reaction from TiO(2) to the oxidized dye, which occurred on a time scale of 0.37 ms.

Photoluminescence of perovskite nanosheets prepared by exfoliation of layered oxides, K2Ln2Ti3O10, KLnNb2O7, and RbLnTa2O7 (Ln: lanthanide ion).

Luminescent perovskite nanosheets were prepared by exfoliation of single- or double-layered perovskite oxides, K2Ln2Ti3O10, KLnNb2O7, and RbLnTa2O7 (Ln: lanthanide ion). The thickness of the individual nanosheets corresponded to those of the perovskite block in the parent layered compounds. Intense red and green emissions were observed in aqueous solutions with Gd1.4Eu0.6Ti3O10- and La0.7Tb0.3Ta2O7-nanosheets, respectively, under UV illumination with energies greater than the corresponding host oxide band gap. The coincidence of the excitation spectrum and the band gap absorbance indicates that the visible emission results from energy transfer within the nanosheet. The red emission intensity of the Gd1.4Eu0.6Ti3O10-nanosheets was much stronger than that of the La0.90Eu0.05Nb2O7-nanosheets reported previously. The strong emission intensity is a result of a two-step energy transfer cascade within the nanosheet from the Ti-O network to Gd(3+) and then to Eu(3+). The emission intensities of the Gd1.4Eu0.6Ti3O10- and La0.7Tb0.3Ta2O7-nanosheets can be modulated by applying a magnetic field (1.3-1.4 T), which brings about a change in orientation of the nanosheets in solution. The emission intensities increased when the excitation light and the magnetic field directions were perpendicular to each other, and they decreased when the excitation and magnetic field were collinear and mutually perpendicular to the direction of detection of the emitted light.

Bidentate dicarboxylate capping groups and photosensitizers control the size of IrO2 nanoparticle catalysts for water oxidation.

Dicarboxylic acid ligands (malonate, succinate, and butylmalonate) stabilize 2 nm diameter IrO2 particles synthesized by hydrolysis of aqueous IrCl(6)2- solutions. Analogous monodentate (acetate) and tridentate (citrate) carboxylate ligands, as well as phosphonate and diphosphonate ligands, are less effective as stabilizers and lead to different degrees of nanoparticle aggregation, as evidenced by transmission electron microscopy. Succinate-stabilized 2 nm IrO2 particles are good catalysts for water photo-oxidation in persulfate/sensitizer solutions. Ruthenium tris(2,2'-bipyridyl) sensitizers containing malonate and succinate groups in the 4,4'-positions are also good stabilizers of 2 nm diameter IrO2 colloids. The excited-state emission of these bound succinate-terminated sensitizer molecules is efficiently quenched on a time scale of approximately 30 ns, most likely by electron transfer to Ir(IV). In 1 M persulfate solutions in pH 5.8 Na2SiF6/NaHCO3 buffer solutions, the excited-state of the bound sensitizer is quenched oxidatively on the time scale of approximately 9 ns. Electron transfer from Ir(IV) to Ru(III) occurs with a first-order rate constant of 8x10(2) s(-1), and oxygen is evolved. The turnover number for oxygen evolution under these conditions was approximately 150. The sensitizer-IrO2 diad is thus a functional catalyst for photo-oxidation of water, and may be a useful building block for overall visible light water splitting systems.

Structural control of the photodynamics of boron-dipyrrin complexes.

Boron-dipyrrin chromophores containing a 5-aryl group with or without internal steric hindrance toward aryl rotation have been synthesized and then characterized via X-ray diffraction, static and time-resolved optical spectroscopy, and theory. Compounds with a 5-phenyl or 5-(4-tert-butylphenyl) group show low fluorescence yields (approximately 0.06) and short excited-singlet-state lifetimes (approximately 500 ps), and decay primarily (>90%) by nonradiative internal conversion to the ground state. In contrast, sterically hindered analogues having an o-tolyl or mesityl group at the 5-position exhibit high fluorescence yields (approximately 0.9) and long excited-state lifetimes (approximately 6 ns). The X-ray structures indicate that the phenyl or 4-tert-butylphenyl ring lies at an angle of approximately 60 degrees with respect to the dipyrrin framework whereas the angle is approximately 80 degrees for mesityl or o-tolyl groups. The calculated potential energy surface for the phenyl-substituted complex indicates that the excited state has a second, lower energy minimum in which the nonhindered aryl ring rotates closer to the mean plane of the dipyrrin, which itself undergoes some distortion. This relaxed, distorted excited-state conformation has low radiative probability as well as a reduced energy gap from the ground state supporting a favorable vibrational overlap factor for nonradiative deactivation. Such a distorted conformation is energetically inaccessible in a complex bearing the sterically hindered o-tolyl or mesityl group at the 5-position, leading to a high radiative probability involving conformations at or near the initial Franck-Condon form of the excited state. These combined results demonstrate the critical role of aryl-ring rotation in governing the excited-state dynamics of this class of widely used dyes.

Tuning Interfacial Electron Transfer in Nanostructured Cuprous Oxide Photoelectrochemical Cells with Charge-Selective Molecular Coatings.

The coating of nanostructured films of cuprous oxide with electroactive molecules strongly affects their photoelectrochemical performance in nonaqueous photocells, with photocurrent density increased up to an order of magnitude relative to bare cuprous oxide films or almost completely suppressed, depending on the choice of molecular adsorbant. Among adsorbants that enhance photocurrent, a strong variance of photoelectrochemical behavior is observed with changes in the molecular structure of the sensitizer, associated with differences in the reorganization energy and molecular size, which are interpreted to enhance forward electron transport and impede electrolyte/photocathode recombination, respectively. These results demonstrate that nanostructured cuprous oxide is a promising cathode material for p-type dye-sensitized solar cells.

Templated electrodeposition and photocatalytic activity of cuprous oxide nanorod arrays.

Cuprous oxide (Cu2O) nanorod arrays have been prepared via a novel templated electrodeposition process and were characterized for their photocatalytic behavior in nonaqueous photoelectrochemical cells. Zinc oxide (ZnO) nanorod films serve as sacrificial templates for the in situ formation of polymer nanopore membranes on transparent conductive oxide substrates. Nitrocellulose and poly(lactic acid) are effective membrane-forming polymers that exhibit different modes of template formation, with nitrocellulose forming conformal coatings on the ZnO surface while poly(lactic acid) acts as an amorphous pore-filling material. Robust template formation is sensitive to the seeding method used to prepare the precursor ZnO nanorod films. Photoelectrochemical cells prepared from electrodeposited Cu2O films using methyl viologen as a redox shuttle in acetonitrile electrolyte exhibit significant charge recombination that can be partially suppressed by a combination of surface passivation methods. Surface-passivated nanostructured Cu2O films show enhanced photocurrent relative to planar electrodeposited Cu2O films of similar thickness. We have obtained the highest photocurrent ever reported for electrodeposited Cu2O in a nonaqueous photoelectrochemical cell.

Solid-state photogalvanic dye-sensitized solar cells.

Photogalvanic cells are photoelectrochemical systems wherein the semiconductor electrode is not a participant in primary photoinduced charge formation. The discovery of photoelectrochemical systems that successfully exploit secondary (thermal) electron injection at dye-semiconductor interfaces may enable studies of electron transfer at minimal driving force for electron injection into the semiconductor. In this study, we have examined thermal electron transfer from molecular sensitizers to nanostructured semiconductor electrodes composed of titanium dioxide nanorods by means of transient spectroscopy and the assembly and testing of photoelectrochemical cells. Electron-accepting molecular dyes have been studied alongside an arylamine electron donor. Thermal injection is estimated for a naphthacenequinone radical anion as a multiexponential decay process with initial decay lifetimes of 6 and 27 ps. The ambient electric field present during charge separation at a surface-adsorbed dye monolayer causes Stark shifts of the radical ion pair absorbance peaks that confounded kinetic estimation of thermal injection for a fullerene sensitizer. Electron-accepting dyes that operate by thermal injection into titanium dioxide function better in solid-state photoelectrochemical cells than in liquid-junction cells due to the kinetic advantage of solid-state cells with respect to photoinduced acceptor-quenching to form the necessary radical anion sensitizers.

Influence of seeding and bath conditions in hydrothermal growth of very thin (∼20 nm) single-crystalline rutile TiO2 nanorod films.

New seeding conditions have been examined for the hydrothermal growth of single-crystalline rutile TiO2 nanorods. Rutile nanorods of ∼20 nm diameter are grown from seed layers consisting of either (A) TiO2 or MnOOH nanocrystals deposited from suspension, or (B) a continuous sheet of TiO2. These seed layers are more effective for seeding the growth of rutile nanorods compared to the use of bare F-SnO2 substrates. The TiO2 sheet seeding allows lower concentration of titanium alkoxide precursor relative to previously reported procedures, but fusion of the resulting TiO2 nanorods into bundles occurs at higher precursor concentration and/or longer growth duration. Performance of polymer-oxide solar cells prepared using these nanorods shows a dependence on the extent of bundling as well as rod height.

Electron transport in acceptor-sensitized polymer-oxide solar cells: the importance of surface dipoles and electron cascade effects.

Fullerene and acenequinone compounds have been examined as electron mediators between a p-type semiconductive polymer and two n-type oxide semiconductors. Composite interlayer materials and photovoltaic test cells were assembled and studied for their fluorescence quenching, current-voltage, and quantum efficiency behavior to characterize the efficacy of the acceptor-sensitizers as electron-selective interlayers. The sensitizers are generally more effective with titanium dioxide than with zinc oxide, due to the difference in magnitude of dipole-induced vacuum level shifts at the respective oxide interfaces. In titanium dioxide-based solar cells, where dipole effects are weak, photovoltage and fill factor increase in a trend that matches the increase in the first reduction potential of the acceptor-sensitizers. Photosensitization of the oxide semiconductor by the acceptor-sensitizers is observed to operate either in parallel with the polymer as an alternate photosensitizer or in series with the polymer in a two-photon process, according to an acceptor-sensitizer's first reduction potential. In zinc oxide-based solar cells, where dipole effects are stronger, the acceptor-sensitizers impaired most devices, which is attributed to an upward shift of the oxide's conduction band edge caused by dipole-induced vacuum level shifts. These results have broad implications for designing electron-selective interlayers and solid-state photocells using sensitized oxide semiconductors.

Electron transfer kinetics in water splitting dye-sensitized solar cells based on core-shell oxide electrodes.

Photoelectrochemical water splitting occurs in a dye-sensitized solar cell when a [Ru(bpy)3]2+-based dye covalently links a porous TiO2 anode film to IrO2 x nH2O nanoparticles. The quantum yield for oxygen evolution is low because of rapid back electron transfer between TiO2 and the oxidized dye, which occurs on a timescale of hundreds of microseconds, When iodide is added as an electron donor, the photocurrent increases, confirming that the initial charge injection efficiency is high. When the porous TiO2 film is coated with a 1-2 nm thick layer of ZrO2 or Nb2O5, both the charge injection rate and back electron transfer rate decrease. The efficiency of the cell increases and then decreases with increasing film thickness, consistent with the trends in charge injection and recombination rates. The current efficiency for oxygen evolution, measured electrochemically in a generator-collector geometry, is close to 100%. The factors that lead to polarization of the photoanode and possible ways to re-design the system for higher efficiency are discussed.

Direct deposition of trivalent rhodium hydroxide nanoparticles onto a semiconducting layered calcium niobate for photocatalytic hydrogen evolution.

Well-dispersed Rh(OH)3 nanoparticles were deposited in the interlayer galleries of a Dion-Jacobson type layered perovskite (ACa2Nb3O10: A=H or K). X-ray photoelectron spectra and zeta potential measurements suggest covalent bonding (Rh-O-Nb) between the nanoparticles and the niobate sheets. After calcination of Rh(OH)3/KCa2Nb3O10 at 350 degrees C in air, interlayer Rh(OH)3 nanoparticles were transformed to Rh2O3 and showed higher photocatalytic activity for hydrogen evolution using methanol as a sacrificial electron donor.

Synthesis of a new trans-A2B2 phthalocyanine motif as a building block for rodlike phthalocyanine polymers.

Polyphthalocyanines have potential application in the development of electronic materials. One-dimensional polyphthalocyanines are accessible through monomers having a trans-A2B2 structure, but the preparation of a truly linear polyphthalocyanine is challenging because of limitations imposed by the geometry of phthalocyanines and the methodology for their synthesis. Benzimidazoporphyrazines are a known class of extra-annulated phthalocyanines. A trans-A2B2 benzimidazoporphyrazine is geometrically suitable for the preparation of rodlike polymers. A new synthesis of benzimidazoporphyrazines is presented as a stepping stone to the synthesis of trans-A2B2 benzimidazoporphyrazines.

Triple-decker sandwich compounds bearing compact triallyl tripods for molecular information storage applications.

The design of redox-active molecules that afford multistate operation and high charge density is essential for molecular information storage applications. Triple-decker sandwich compounds composed of two lanthanide metal ions and three porphyrinic ligands exhibit a large number of oxidation states within a relatively narrow electrochemical window. High charge density requires a small footprint upon tethering triple deckers to an electroactive surface. All triple deckers examined to date for information storage have been tethered via the terminal ligand and have exhibited large footprints (approximately 670 A2). Five new homonuclear (Eu or Ce) triple deckers have been prepared (via statistical or rational methods) to examine the effect of tether attachment site on molecular footprint. Three triple deckers are tethered via the terminal ligand (porphyrin) or central ligand (porphyrin or imidazophthalocyanine), whereas two triple deckers each bear two tethers, one at each terminal ligand. The tether is a compact triallyl tripod. Monolayers of the triple deckers on Si(100) were examined by electrochemical and FTIR techniques. Each triple decker exhibited the expected four resolved voltammetric waves, owing to formation of the mono-, di-, tri-, and tetracations. The electrochemical studies of surface coverage (gamma, obtained by integrating the voltammetric waves) reveal that coverages approaching 10(-10) mol cm(-2), corresponding to a molecular footprint of approximately 170 A2, are readily achieved for all five of the triple deckers. The surface coverage observed for the tripodal functionalized triple deckers is approximately 4-fold higher than that obtained for monopodal-functionalized triple deckers (carbon, oxygen, or sulfur anchor atoms) attached to either Si(100) or Au(111). The fact that similar, relatively high, surface coverages can be achieved regardless of the location (or number) of the tripodal tether indicates that the tripodal functionalization, rather than the location of the tether, is the primary determinant of the packing density.

Diverse redox-active molecules bearing identical thiol-terminated tripodal tethers for studies of molecular information storage.

To examine the effects of molecular structure on charge storage in self-assembled monolayers (SAMs), a family of redox-active molecules has been prepared wherein each molecule bears a tether composed of a tripodal linker with three protected thiol groups for surface attachment. The redox-active molecules include ferrocene, zinc porphyrin, ferrocene-zinc porphyrin, magnesium phthalocyanine, and triple-decker lanthanide sandwich coordination compounds. The tripodal tether is based on a tris[4-(S-acetylthiomethyl)phenyl]-derivatized methane. Each redox-active unit is linked to the methane vertex by a 4,4'-diphenylethyne unit. The electrochemical characteristics of each compound were examined in solution and in SAMs on Au. Redox-kinetic measurements were also performed on the SAMs (with the exception of the magnesium phthalocyanine) to probe (1) the rate of electron transfer in the presence of an applied potential and (2) the rate of charge dissipation after the applied potential is disconnected. The electrochemical studies of the SAMs indicate that the tripodal tether provides a more robust anchor to the Au surface than does a tether with a single site of attachment. However, the electron-transfer and charge-dissipation characteristics of the two tethers are generally similar. These results suggest that the tripodal tether offers superior stability characteristics without sacrificing electrochemical performance.

A tin-complexation strategy for use with diverse acylation methods in the preparation of 1,9-diacyldipyrromethanes.

The acylation of dipyrromethanes to form 1,9-diacyldipyrromethanes is an essential step in the rational synthesis of porphyrins. Although several methods for acylation are available, purification is difficult because 1,9-diacyldipyrromethanes typically streak extensively upon chromatography and give amorphous powders upon attempted crystallization. A solution to this problem has been achieved by reacting the 1,9-diacyldipyrromethane with Bu(2)SnCl(2) to give the corresponding dibutyl(5,10-dihydrodipyrrinato)tin(IV) complex. The reaction is selective for dipyrromethanes that bear acyl groups at both the 1- and 9-positions but otherwise is quite tolerant of diverse substituents. The diacyldipyrromethane-tin complexes are stable to air and water, are highly soluble in common organic solvents, crystallize readily, and chromatograph without streaking. Four methods (Friedel-Crafts, Grignard, Vilsmeier, benzoxathiolium salt) were examined for the direct 1,9-diacylation of a dipyrromethane or the 9-acylation of a 1-acyldipyrromethane. In each case, treatment of the crude reaction mixture with Bu(2)SnCl(2) and TEA at room temperature enabled facile isolation of multigram quantities of the 1,9-diacyldipyrromethane-tin complex. The diacyldipyrromethane-tin complexes could be decomplexed with TFA in nearly quantitative yield. Alternatively, use of a diacyldipyrromethane-tin complex in a porphyrin-forming reaction (reduction with NaBH(4), acid-catalyzed condensation with a dipyrromethane, DDQ oxidation) afforded the desired free base porphyrin in yield comparable to that obtained from the uncomplexed diacyldipyrromethane. The acylation/tin-complexation strategy has been applied to a bis(dipyrromethane) and a porphyrin-dipyrromethane. In summary, the tin-complexation strategy has broad scope, is compatible with diverse acylation methods, and greatly facilitates access to 1,9-diacyldipyrromethanes.

Glaser-mediated synthesis and photophysical characterization of diphenylbutadiyne-linked porphyrin dyads.

The Pd-mediated Glaser coupling of a zinc monoethynyl porphyrin and a magnesium monoethynyl porphyrin affords a mixture of three 4,4'-diphenylbutadiyne-linked dyads comprised of two zinc porphyrins (Zn-pbp-Zn), two magnesium porphyrins (Mg-pbp-Mg), and one metalloporphyrin of each type (Zn-pbp-Mg). The latter is easily isolated due to the greater polarity of the magnesium versus the zinc chelate. Exposure of Zn-pbp-Mg to silica gel results in selective demetalation, affording Zn-pbp-Fb where Fb = free base porphyrin. This synthesis route employs the magnesium porphyrin as a latent form of the Fb porphyrin, thereby avoiding copper insertion during the Glaser reaction, and as a polar entity facilitating separation. The absorption spectrum of Zn-pbp-Mg or Zn-pbp-Fb is the sum of the spectra of the component parts, while in each case the fluorescence spectrum upon illumination of the Zn porphyrin is dominated by emission from the Mg or Fb porphyrin. Time-resolved absorption spectroscopy shows that the energy-transfer rate constants are (11 ps)(-1) and (37 ps)(-1) for Zn-pbp-Mg and Zn-pbp-Fb, respectively, corresponding to energy-transfer quantum yields of 0.995 and 0.983, respectively. The calculated Förster through-space rates are (1900 ps)(-1) and (1100 ps)(-1) for Zn-pbp-Mg and Zn-pbp-Fb, respectively. Accordingly, the through-bond process dominates for both dyads with a through-bond:through-space energy-transfer ratio of > or =97:1. Collectively, the studies show that the 4,4'-diphenylbutadiynyl linker supports fast and efficient energy transfer between Zn and Mg or Fb porphyrins.