Ultrafast photodriven intramolecular electron transfer from an iridium-based water-oxidation catalyst to perylene diimide derivatives.

Photodriving the activity of water-oxidation catalysts is a critical step toward generating fuel from sunlight. The design of a system with optimal energetics and kinetics requires a mechanistic understanding of the single-electron transfer events in catalyst activation. To this end, we report here the synthesis and photophysical characterization of two covalently bound chromophore-catalyst electron transfer dyads, in which the dyes are derivatives of the strong photooxidant perylene-3,4:9,10-bis(dicarboximide) (PDI) and the molecular catalyst is the Cp*Ir(ppy)Cl metal complex, where ppy = 2-phenylpyridine. Photoexcitation of the PDI in each dyad results in reduction of the chromophore to PDI(•-) in less than 10 ps, a process that outcompetes any generation of (3*)PDI by spin-orbit-induced intersystem crossing. Biexponential charge recombination largely to the PDI-Ir(III) ground state is suggestive of multiple populations of the PDI(•-)-Ir(IV) ion-pair, whose relative abundance varies with solvent polarity. Electrochemical studies of the dyads show strong irreversible oxidation current similar to that seen for model catalysts, indicating that the catalytic integrity of the metal complex is maintained upon attachment to the high molecular weight photosensitizer.

Photoinduced singlet charge transfer in a ruthenium(II) perylene-3,4:9,10-bis(dicarboximide) complex.

Elucidation of photoinduced charge transfer behavior in organic dye/metal hybrids is important for developing photocatalytic systems for solar energy conversion. We report the synthesis and photophysical characterization of a perylene-3,4:9,10-bis(dicarboximide) (PDI)-ruthenium(II) complex, bis-PDI-2,2'-bipyridineRu(II)Cl(2)(CN(t)butyl)(2), which has favorable energetics, ΔG(CS) ≈ -1.0 eV, for singlet electron transfer from the Ru complex to PDI. Time-resolved optical spectroscopy reveals that upon selective photoexcitation of PDI, ultrafast charge transfer (<150 fs) from the Ru complex to (1*)PDI generates the Ru(III)-PDI(-•) ion pair. The resulting vibrationally hot Ru(III)-PDI(-•) ion pair exhibits fast relaxation (τ = 3.9 ps) and charge recombination (τ(CR) = 63 ps). Our experimental and computational (DFT and TDDFT) studies show that energy-preserving photodriven singlet electron transfer can dominate in properly designed organic dye/metal complexes, making them of particular interest for use in artificial photosynthetic systems for solar fuels formation.

Synthesis, characterization, and photoinduced energy and electron transfer in a supramolecular tetrakis (ruthenium(II) phthalocyanine) perylenediimide pentad.

Metal coordination was probed as a versatile approach for designing a novel electron donor/acceptor hybrid [PDIpy(4){Ru(CO)Pc}(4)] (1), in which four pyridines placed at the bay region of a perylenediimides (PDIpy(4)) coordinate with four ruthenium phthalocyanine units [Ru(CO)Pc]. This structural motif was expected to promote strong electronic coupling between the electron donors and the electron acceptor, a hypothesis that was confirmed in a full-fledged physicochemical investigation focusing on the ground and excited state reactivities. As far as the ground state is concerned, absorption and electrochemical assays indeed reveal a notable redistribution of electron density, that is, from the electron-donating [Ru(CO)Pc] to the electron-accepting PDIpy(4). The most important thing to note in this context is that both the [Ru(CO)Pc] oxidation and the PDIpy(4) reduction are rendered more difficult in 1 than in the individual building blocks. Likewise, in the excited state, strong electronic communication is the inception for a rapid charge-transfer process in photoexcited 1. Regardless of exciting [Ru(CO)Pc] or PDIpy(4), spectral characteristics of the [RuPc] radical cation (broad absorptive features from 425 to 600 nm with a maximum at 575 nm, as well as a band centered at 725 nm) and of the PDI radical anion (780 nm maximum) emerge. The correspondingly formed radical ion pair state lasts for up to several hundred picoseconds in toluene, for example. On the other hand, employing more polar solvents, such as dichloromethane, destabilizes the radical ion pair state.

Photophysics and redox properties of rylene imide and diimide dyes alkylated ortho to the imide groups.

Ruthenium-catalyzed C-H bond activation was used to directly attach phenethyl groups derived from styrene to positions ortho to the imide groups in a variety of rylene imides and diimides including naphthalene-1,8-dicarboximide (NMI), naphthalene-1,4:5,8-bis(dicarboximide) (NI), perylene-3,4-dicarboximide (PMI), perylene-3,4:9,10-bis(dicarboximide) (PDI), and terrylene-3,4:11,12-bis(dicarboximide) (TDI). The monoimides were dialkylated, while the diimides were tetraalkylated, with the exception of NI, which could only be dialkylated due to steric hindrance. The absorption, fluorescence, transient absorption spectra, and lowest excited singlet state lifetimes of these chromophores, with the exception of NI, are nearly identical to those of their unsubstituted parent chromophores. The reduction potentials of the dialkylated chromophores are approximately 100 mV more negative and oxidation potentials are approximately 40 mV less positive than those of the parent compounds, while the corresponding potentials of the tetraalkylated compounds are approximately 200 mV more negative and approximately 100 mV less positive than those of their parent compounds, respectively. Continuous wave electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) data on the radical anion of PDI reveals spin density on the perylene-core protons as well as on the beta-protons of the phenethyl groups. The phenethyl groups enhance the otherwise poor solubility of the bis(dicarboximide) chromophores and only weakly perturb the photophysical and redox properties of the parent molecules, rendering these derivatives and related molecules of significant interest to solar energy conversion.

Measurement of both the equilibrium constant and rate constant for electronic energy transfer by control of the limiting kinetic regimes.

Electronic energy transfer can fall into two limiting cases. When the rate of the energy transfer back reaction is much faster than relaxation of the acceptor excited state, equilibrium between the donor and acceptor excited states is achieved and only the equilibrium constant for the energy transfer can be measured. When the rate of the back reaction is much slower than relaxation of the acceptor, the energy transfer is irreversible and only the forward rate constant can be measured. Herein, we demonstrate that with trans-[Cr(d(4)-cyclam)(CN)(2)](+) as the donor and either trans-[Cr([15]ane-ane-N(4))(CN)(2)](+) or trans-[Cr(cyclam)(CN)(2)](+) as the acceptor, both limits can be obtained by control of the donor concentration. The equilibrium constant and rate constant for the case in which trans-[Cr([15]ane-ane-N(4))(CN)(2)](+) is the acceptor are 0.66 and 1.7 x 10(7) M(-1) s(-1), respectively. The equilibrium constant is in good agreement with the value of 0.60 determined using the excited state energy gap between the donor and acceptor species. For the thermoneutral case in which trans-[Cr(cyclam)(CN)(2)](+) is the acceptor, an experimental equilibrium constant of 0.99 was reported previously, and the rate constant has now been measured as 4.0 x 10(7) M(-1) s(-1).

Effects of steric constraint on Chromium(III) complexes of tetraazamacrocycles. 3. Insights into the temperature-dependent radiationless deactivation of the 2Eg (Oh) excited state of trans-[Cr(N4)(CN)2]+ complexes.

Macrocyclic complexes of the type trans-[Cr(N4)(CN)2]+, where N4 = cyclam, 1,11-C3-cyclam, and 1,4-C2-cyclam demonstrate significant variation in their room-temperature excited-state behavior; namely, the lifetimes of the 2Eg (Oh) excited states are 335, 23, and 0.24 micros, respectively. The lifetimes of these complexes have been measured in acidified H2O/dimethyl sulfoxide over the temperature range between -30 and +95 degrees C. Arrhenius activation parameters were calculated from these data. There was very little variation in the values of the Arrhenius preexponential factor between these three complexes, whereas the value of Ea is 40.6 kJ/mol for the cyclam complex, 35.5 kJ/mol for the 1,11-C3-cyclam complex, and 22.3 kJ/mol for the 1,4-C2-cyclam complex. Thus, differences in the room-temperature excited-state lifetimes can be rationalized based on the competition between thermally independent nonradiative relaxation and a thermally activated channel. To test whether a photodissociation mechanism involving Cr-macrocyclic N bond cleavage is a plausible explanation for the thermally activated relaxation pathway, samples of the cyclam complex were photolyzed in acidified D(2)O. A marked increase in the lifetime after photolysis demonstrated the occurrence of photodeuteration and thus a likely photodissociation of a macrocyclic N.

Effects of steric constraint on chromium(III) complexes of tetraazamacrocycles, 2. Comparison of the chemistry and photobehavior of the trans-dichloro- and trans-dicyano- complexes of cyclam, 1,4-C2-cyclam, and 1,11-C3-cyclam.

The synthesis and characterization of several Cr(III) complexes of the constrained macrocyclic ligand 1,11-C3-cyclam (1,4,8,11-tetraazabicyclo[9.3.3]heptadecane) is reported. Only trans complexes are formed, and the structure of trans-[Cr(1,11-C3-cyclam)Cl2]PF6 is presented. The chemical and photophysical behavior of the 1,11-C3-cyclam complexes are compared with those of the corresponding cyclam (1,4,8,11 tetraazacyclotetradecane) and 1,4-C2-cyclam (1,4,8,11-tetraazabicyclo[10.2.2]hexadecane) complexes. The aquation rate of trans-[Cr(1,11-C3-cyclam)Cl2]+ is similar to that of the corresponding 1,4-C2-cyclam complex and is more than 5 orders of magnitude faster than the cyclam counterpart. A monotonic increase in the extinction coefficient is observed on going from the cyclam complexes to the 1,11-C3-cyclam complexes to the 1,4-C2-cyclam complexes, and this is related to the degree of centrosymmetry in each complex. The trans-[Cr(1,11-C3-cyclam)(CN)2]+ complex is a weak emitter in aqueous solution with a room-temperature emission maximum at 724 nm (tau=23 micros). Like the corresponding 1,4-C2-cyclam complex (tau=0.24 micros), the 1,11-C3-cyclam complex shows no deuterium-isotope effect in room-temperature solution. This is in marked contrast to the corresponding cyclam complex which has an emission lifetime of 335 micros and a significant deuterium isotope effect in room-temperature solution. Low temperature (77K) data are also presented in an attempt to understand the differences in photophysical behavior.