Dendritic metalloporphyrin-fullerene conjugates: changing the microenvironment around redox-active centers and its impact on charge-transfer reactions.

Photophysical investigations on a series of (2,4,6)-tris-substituted metalloporphyrin-fullerene conjugates revealed the effects of an electron-rich microenvironment surrounding the electron-donating porphyrin as a function of the metal center. On one hand, for all conjugates-water-soluble and non-water-soluble-ultrafast charge separation was observed upon photoexcitation. On the other hand, when examining the charge recombination dynamics for the non-water-soluble conjugates it becomes obvious that the (2,4,6)-tris-substitution stabilizes the radical-ion-pair state relative to the mono-substitution in the ortho-, meta-, and para-position. The more efficient protection of the electron-donating porphyrin from solvation is thought to be the major cause for this impact. Nevertheless, the situation is slightly different for the water-soluble conjugates. At first glance, the radical-ion-pair state lifetimes are, also in the case of the (2,4,6)-tris-substitution, longer than for the mono-substituted ortho-, meta- and para-conjugates. Upon closer inspection, they fail, however, to exhibit any metal dependence. Competing with the protection from solvation of the dendrons, dipole-charge interactions impact the stabilization in the polar aqueous environment and, in turn, become the dominant force governing the electron-transfer dynamics.

Dendronized fullerene-porphyrin conjugates in ortho, meta, and para positions: a charge-transfer assay.

The physicochemical characterization, that is, ground and excited state, of a new series of dendronized porphyrin/fullerene electron donor-acceptor conjugates in nonaqueous and aqueous environments is reported. In contrast to previous work, we detail the charge-separation and charge-recombination dynamics in zinc and copper metalloporphyrins as a function of first- and second-generation dendrons as well as a function of ortho, meta, and para substitution. Both have an appreciable impact on the microenvironments of the redox-active constituents, namely the porphyrins and the fullerenes. As a matter of fact, the resulting charge-transfer dynamics were considerably impacted by the interplay between the associated forces that reach from dendron-induced shielding to dipole-charge interactions.

A charge-transfer challenge: combining fullerenes and metalloporphyrins in aqueous environments.

A series of truly water-soluble C(60)/porphyrin electron donor-acceptor conjugates has been synthesized to serve as powerful mimics of photosynthetic reaction centers. To this end, the overall water-solubility of the conjugates was achieved by adding hydrophilic dendrimers of different generations to the porphyrin moiety. An important variable is the metal center of the porphyrin; we examined zinc(II), copper(II), cobalt(II), nickel(II), iron(III), and manganese(III). The first insights into electronic communication between the electron donors and the electron acceptors came from electrochemical assays, which clearly indicate that the redox processes centered either on C(60) or the porphyrins are mutually affected. Absorption measurements, however, revealed that the electronic communication in terms of, for example, charge-transfer features, remains spectroscopically invisible. The polar environment that water provides is likely to be a cause of the lack of detection. Despite this, transient absorption measurements confirm that intramolecular charge separation processes in the excited state lead to rapid deactivation of the excited states and, in turn, afford the formation of radical ion pair states in all of the investigated cases. Most importantly, the lifetimes of the radical ion pairs were found to depend strongly on several aspects. The nature of the coordinated metal center and the type of dendrimer have a profound impact on the lifetime. It has been revealed that the nature/electronic configuration of the metal centers is decisive in powering a charge recombination that either reinstates the ground state or any given multiplet excited state. Conversely, the equilibrium of two opposing forces in the dendrimers, that is, the interactions between their hydrophilic regions and the solvent and the electronic communication between their hydrophobic regions and the porphyrin and/or fullerene, is the key to tuning the lifetimes.

Excited state kinetics in crystalline solids: self-quenching in nanocrystals of 4,4'-disubstituted benzophenone triplets occurs by a reductive quenching mechanism.

We report an efficient triplet state self-quenching mechanism in crystals of eight benzophenones, which included the parent structure (1), six 4,4'-disubstituted compounds with NH(2) (2), NMe(2) (3), OH (4), OMe (5), COOH (6), and COOMe (7), and benzophenone-3,3',4,4'-tetracarboxylic dianhydride (8). Self-quenching effects were determined by measuring their triplet-triplet lifetimes and spectra using femtosecond and nanosecond transient absorption measurements with nanocrystalline suspensions. When possible, triplet lifetimes were confirmed by measuring the phosphorescence lifetimes and with the help of diffusion-limited quenching with iodide ions. We were surprised to discover that the triplet lifetimes of substituted benzophenones in crystals vary over 9 orders of magnitude from ca. 62 ps to 1 ms. In contrast to nanocrystalline suspensions, the lifetimes in solution only vary over 3 orders of magnitude (1-1000 µs). Analysis of the rate constants of quenching show that the more electron-rich benzophenones are the most efficiently deactivated such that there is an excellent correlation, ρ = -2.85, between the triplet quenching rate constants and the Hammet σ(+) values for the 4,4' substituents. Several crystal structures indicate the existence of near-neighbor arrangements that deviate from the proposed ideal for "n-type" quenching, suggesting that charge transfer quenching is mediated by a relatively loose arrangement.

Oxyallyl exposed: an open-shell singlet with picosecond lifetimes in solution but persistent in crystals of a cyclobutanedione precursor.

Photoinduced decarbonylation of 2,4-bis(spirocyclohexyl)-1,3-cyclobutanedione 1 in the crystalline solid state resulted in formation of a deep blue transient with λ(max) = 550 nm and a half-life of 42 min at 298 K, identified as kinetically stabilized oxyallyl. Support for an open-shell singlet species was obtained by spectroscopic analysis and (4/4) CASSCF calculations with the 6-31+G(d) basis set and multireference MP2 corrections. The electronic spectrum of the singlet biradical, confirmed by femtosecond pump-probe studies in solution, was matched by coupled cluster calculations with single and double corrections.

A fully conjugated TTF-π-TCAQ system: synthesis, structure, and electronic properties.

The synthesis of the first fully conjugated tetrathiafulvalene-tetracyano-p-quinodimethane ((TTF)-TCNQ)-type system has been carried out by means of a Julia-Kocienski olefination reaction. In particular, a tetracyanoanthraquinodimethane (TCAQ) formyl derivative and two new sulfonylmethyl-exTTFs (exTTF = 2-[9-(1,3-dithiol-2-ylidene)anthracen-10(9H)-ylidene]-1,3-dithiole)--prepared as new building blocks--were linked. A variety of experimental conditions reveal that the use of sodium hexamethyldisilazane (NaHMDS) as base in THF afforded the E olefins with excellent stereoselectivity. Theoretical calculations at the B3LYP/6-31G** level point to highly distorted exTTF and TCAQ that form an almost planar stilbene unit between them. Although calculations predicted appreciable electronic communication between the donor and the acceptor, cyclic voltammetric studies did not substantiate this effect. It was only in photophysical assays that the electronic communication emerged in the form of a charge-transfer (CT) absorption and emission. Once photoexcited (i.e., the locally excited state or excited charge-transfer state), an ultrafast, subpicosecond charge separation leads to a radical ion pair state in which the spectroscopic features of the radical cation of exTTF as well as the radical anion of TCAQ are discernable. The radical ion pair is metastable and undergoes a fast ((1.0±0.2) ps) charge recombination to reconstitute the electronic ground state. Such ultrafast charge separation and recombination processes come as a consequence of the very short vinyl linkage between the two electroactive units.

Efficient utilization of higher-lying excited states to trigger charge-transfer events.

Several new fullerene-heptamethine conjugates, which absorb as far as into the infrared spectrum as 800 nm, have been synthesized and fully characterized by physicochemical means. In terms of optical and electrochemical characteristics, appreciable electronic coupling between both electroactive species is deduced. The latter also reflect the excited-state features. To this end, time-resolved, transient absorption measurements revealed that photoexcitation is followed by a sequence of charge-transfer events which evolve from higher singlet excited states (i.e., S(2)--fast charge transfer) and the lowest singlet excited state of the heptamethine cyanine (i.e., S(1)--slow charge transfer), as the electron donor, to either a covalently linked C(60) or C(70), as the electron acceptor. Finally, charge transfer from photoexcited C(60)/C(70) completes the charge-transfer sequence. The slow internal conversion within the light-harvesting heptamethine cyanine and the strong electronic coupling between the individual constituents are particularly beneficial to this process.

Dendronizing and metalating trans-2 C60 tetraaryl porphyrins--a versatile approach toward water-soluble donor-acceptor conjugates.

We have realized for the first time a series of truly water-soluble and tightly coupled porphyrin/C(60) electron-donor-acceptor conjugates in which the charge separation and charge recombination dynamics are controlled by modifying the nature of the dendrimer and/or the choice of the central metal atom.

Dendritic porphyrin-fullerene conjugates: efficient light-harvesting and charge-transfer events.

A novel dendritic C(60)-H(2)P-(ZnP)(3) (P=porphyrin) conjugate gives rise to the successful mimicry of the primary events in photosynthesis, that is, light harvesting, unidirectional energy transfer, charge transfer, and charge-shift reactions. Owing, however, to the flexibility of the linkers that connect the C(60), H(2)P, and ZnP units, the outcome depends strongly on the rigidity/viscosity of the environment. In an agar matrix or Triton X-100, time-resolved transient absorption spectroscopic analysis and fluorescence-lifetime measurements confirm the following sequence. Initially, light harvesting is seen by the peripheral C(60)-H(2)P- *(ZnP)(3) conjugate. Once photoexcited, a unidirectional energy transfer funnels the singlet excited-state energy to H(2)P to form C(60)-*(H(2)P)-(ZnP)(3), which powers an intramolecular charge transfer that oxidizes the photoexcited H(2)P and reduces the adjacent C(60) species. In the correspondingly formed (C(60))(*-)-(H(2)P)(*+)-(ZnP)(3) conjugate, an intramolecular charge-shift reaction generates (C(60))(*-)-H(2)P-(ZnP)(3) (.+), in which the radical cation resides on one of the three ZnP moieties, and for which lifetimes of up to 460 ns are found. On the other hand, investigations in organic media (i.e., toluene, THF, and benzonitrile) reveal a short cut, that is, the peripheral ZnP unit reacts directly with C(60) to form (C(60))(*-)-H(2)P-(ZnP)(3) (*+). Substantial configurational rearrangements- placing ZnP and C(60) in proximity to each other-are, however, necessary to ensure the required through space interactions (i.e., close approach). Consequently, the lifetime of (C(60))(*-)-H(2)P-(ZnP)(3) (*+) is as short as 100 ps in benzonitrile.

trans-2 addition pattern to power charge transfer in dendronized metalloporphyrin C60 conjugates.

Coordinating different transition metals--manganese(III), iron(III), nickel(II), and copper(II)--by a dendronized porphyrin afforded a new family of redox-active metalloporphyrins to which C(60) was attached as a ground-state electron acceptor. Such a strategy introduced an additional center of redoxactivity, that is, a change of the oxidation state of the metal. Cyclic voltammetry and absorption/fluorescence measurements provided support for mutual interactions between the redox-active constituents in the ground state. In particular, slightly anodic shifted reduction potentials/cathodic shifted oxidation potentials and the occurrence of new charge transfer features in the 700-900 nm range prompt to sizable electronic coupling in the range of 300 cm(-1). Photophysical means--steady-state/time-resolved fluorescence and transient absorption measurements--shed light on the excited-state interactions. To this end, we have added pulse radiolytic investigations to characterize the radical cation (i.e., metalloporphyrins) and radical anion (i.e., fullerene) characteristics. Pi-pi stacking of the excited state electron donor and the electron acceptor is key to overcome the intrinsically fast deactivation of the excited states in these metalloporphyrins and to power an exothermic charge transfer. The lifetimes of the rapidly and efficiently generated radical ion pair states, which range from 15 to >3000 ps, revealed several important trends. First, they were found to depend on the solvent polarity. Second, the nature of the transition metal plays a similarly decisive role. It is important that the product of charge recombination, namely tripmultiplet excited states versus ground state, had a great impact. Finally, a correlation between the charge transfer rate (i.e., charge separation and charge recombination) and the free energy change for the underlying reaction reveals a parabolic dependence with parameters of the reorganization energy (0.84 eV) and electronic coupling (70 cm(-1)) closely resembling that seen for the zinc(II) and free base analogues.

Tuning charge transfer energetics in reaction center mimics via T(h)-functionalization of fullerenes.

We have introduced an approach of mono- and hexakis-adducts of C(60) involving a T(h)-symmetrical addition pattern, where up to 12 ferrocene or 10 ferrocene and one porphyrin units are linked flexibly to C(60) with the objective to systematically raise the energy of the radical ion pair state. A detailed electrochemical and photophysical investigation has shed light onto charge transfer events that depend largely on (i) the functionalization pattern of C(60), (ii) the donor strength of the donor, (iii) the excited-state energy of the predominant chromophore, and (iv) the solvent polarity. Considering (i)-(iv), the presence of the porphyrins is key to providing sufficient driving forces for affording spatially separated radical ion pair states. An ideal scenario, that is, testing ZnP-C(60)-(Fc)(10) (19) in benzonitrile and DMF, allows storing nearly 1.7 eV in a nanosecond lived radical ion pair state. In this context, the flexible linkage, powering a through space charge transfer, prevents, however, stabilization of the radical ion pair state beyond nanoseconds.

Contrasting photodynamics between C60-dithiapyrene and C60-pyrene dyads.

The photodynamics of a C60-dithiapyrene donor-acceptor conjugate were compared with the corresponding C60-pyrene conjugate. The photoinduced charge separation and subsequent charge recombination processes were examined by time-resolved fluorescence measurements on the picosecond timescale and transient absorption measurements on the picosecond and microsecond timescales with detection in the visible and near-infrared regions. We have observed quite long lifetimes (i.e., up to 1.01 ns) for the photogenerated charge-separated state in a C60-dithiapyrene dyad without the need for i) a long spacer between the two moieties, or ii) a gain in aromaticity in the radical ion pair.

A tightly coupled bis(zinc(II) phthalocyanine)-perylenediimide ensemble to yield long-lived radical ion pair states.

A conjugated donor-acceptor array composed of two phthalocyanines connected to the bay region of a perylenediimide is assembled by using palladium chemistry. Excitation of the phthalocyanine produces a nanosecond lived charge-separated state.