Functional molecular wires are essential for the development of molecular electronics. Charge transport through molecules occurs primarily by means of two mechanisms, coherent superexchange and incoherent charge hopping. Rates of charge transport through molecules in which superexchange dominates decrease approximately exponentially with distance, which precludes using these molecules as effective molecular wires. In contrast, charge transport rates through molecules in which incoherent charge hopping prevails should display nearly distance independent, wirelike behavior. We are now able to determine how each mechanism contributes to the overall charge transport characteristics of a donor-bridge-acceptor (D-B-A) system, where D = phenothiazine (PTZ), B = p-oligophenylene, and A = perylene-3,4:9,10-bis(dicarboximide) (PDI), by measuring the interaction between two unpaired spins within the system's charge separated state via magnetic field effects on the yield of radical pair and triplet recombination product.

Reported herein is a combination of experimental and DFT/TDDFT theoretical investigations of the ground and excited states of 1,4,8,11,15,18,22,25-Octabutoxyphthalocyaninato-nickel(II), NiPc(BuO)(8), and the dynamics of its deactivation after excitation into the S(1)(pi,pi) state in toluene solution. According to X-ray crystallographic analysis NiPc(BuO)(8) has a highly saddled structure in the solid state. However, DFT studies suggest that in solution the complex is likely to flap from one D(2)(d)-saddled conformation to the opposite one through a D(4)(h)-planar structure. The spectral and kinetic changes for the complex in toluene are understood in terms of the 730 nm excitation light generating a primarily excited S(1) (pi,pi) state that transforms initially into a vibrationally hot (3)(d(z)2,d(x)2(-)(y)2) state. Cooling to the zeroth state is complete after ca. 8 ps. The cold (d,d) state converted to its daughter state, the (3)LMCT (pi,d(x)2(-)(y)2), which itself decays to the ground state with a lifetime of 640 ps. The proposed deactivation mechanism applies to the D(2)(d)-saddled and the D(4)(h)-planar structure as well. The results presented here for NiPc(BuO)(8) suggest that in nickel phthalocyanines the (1,3)LMCT (pi,d(x)2(-)(y)2) states may provide effective routes for radiationless deactivation of the (1,3)(pi,pi) states.

An attempt is described to replace the present definition of the kilogram with the mass of a certain number of silicon atoms. A prerequisite for this is that the Avogadro constant, N A , is determined with a relative uncertainty of better than 2 × 10 −8. For the determination, silicon crystals are used. However, the difficulty arising thereby is the measurement of the average molar mass of natural Si. Consequently, a worldwide collaboration has been launched to produce approximately a 5 kg 28 Si single crystal with an enrichment factor greater than 99.985% and of sufficient chemical purity so that it can be used to determine N A with the targeted relative measurement uncertainty mentioned above. In the following, the first successful tests of all technological steps will be reported (enrichment of SiF 4 , distillation into silane and chemical purification, chemical vapour deposition of polycrystalline 28 Si, floating zone growth of a dislocation-free single crystal) and new equipment for the production of high-purity 28 Si with an enrichment of not less than 99.99% will be described. All steps are well defined by a Technical Road Map (TRM28) and all key results are measured by new mass spectrometric, IR spectroscopic and other chemical and physical methods, such as Hall effect, photoluminescence, laser scattering and x-ray topographic methods (TRM for Analytical Monitoring and Certification, TRM28-AMC). The initial enrichment of the gas is >0.999 95 and the depletion during the entire process is <0.000 05. The isotopic homogeneity is checked by natural Si crystal growth and does, in the enriched sphere, not

Photoexcitation of chromophoric dimers constrained to a symmetric π-stacked geometry by their molecular structure usually produce excimers independent of solvent polarity, while dimers with edge-to-edge perpendicular π systems undergo excited-state symmetry breaking in highly polar solvents leading to intradimer charge separation. We present direct evidence for symmetry breaking in the lowest excited singlet state of a symmetric cofacial dimer of 9-(N-pyrrolidinyl)-1,6-bis(3,5-di-tert-butylphenoxy)perylene-3,4-dicarboximide (5PMI) in the lowpolarity solvent toluene to produce a radical ion pair quantitatively. This dimer, cof-5PMI 2 , was synthesized by attaching two 5PMI chromophores via imide groups to a xanthene spacer. For comparison, a linear symmetric dimer, lin-5PMI 2 , was prepared in which the 5PMI chromophores are linked end-to-end via a N-N single bond between their imides. The edge-to-edge π systems of the 5PMI chromophores within lin-5PMI 2 are perpendicular to one another. Ground-state absorption spectra of both 5PMI dimers show exciton coupling, which is consistent with the orientation of the 5PMI chromophores relative to one another. Ultrafast transient absorption spectroscopy following excitation of the dimers with 400-nm, 80-fs laser pulses shows that quantitative intradimer electron transfer occurs in cof-5PMI 2 in toluene with τ = 0.9 ps, followed by charge recombination to ground state with τ = 780 ps. Similar measurements on lin-5PMI 2 reveal that photoinduced electron transfer does not occur in toluene, but occurs in more polar solvents such as 2-methyltetrahydrofuran, wherein τ = 4.5 ps for charge separation and τ = 660 ps for charge recombination. Excited-state symmetry breaking in 5PMI dimers provides new routes to biomimetic charge separation and storage assemblies that can be more easily prepared and modified than those based on multiple tetrapyrrole macrocycles.

All photosynthetic reaction centers (RCs) have two parallel sets of electron transfer cofactors that cross the membrane. In quinone-type RCs (including photosystem II (PSII)), however, only one pathway (the active branch) is used for electron transfer. Since the electron transfer cofactors of each pathway have nearly identical distance and orientation relationships, it is assumed that local differences in protein environment determine the directionality of electron transfer. To understand further the factors that affect energy distribution among the PSII RC cofactors, we altered the PSII RC cofactor symmetry by replacing the inactive-branch pheophytin (Pheo) with a chlorophyll (Chl). We mutated the D1-L210 residue to a histidine (D1-L210H) to provide a Mg ligand for Chl. Analyses of the pigment composition of D1-L210H RCs indicated that the inactivebranch Pheo had been replaced by a Chl. Comparisons of wild-type and D1-L210 transient absorption spectra confirmed that the red-shifted Pheo Qx absorption band (543.5 nm) belonged to the active-branch Pheo. Surprisingly, intact D1-L210H PSII complexes were unable to evolve oxygen, lacked Chl variable fluorescence, (following a flash), and were unable to photoaccumulate reduced Qa, indicating that electron transfer in D1-L210H PSII complexes was severely perturbed. The kinetics of primary charge separation, however, were not substantially altered in D1-L210H RCs, indicating that the Chl substitution had not perturbed the energetics of the primary electron donor/acceptor pair. Significantly, intact D1-L210H PSII core complexes had a substantially increased and red-shifted Chl fluorescence emission band attributed to fluorescence from Chl's of the distal antenna complex as well as a blue-shifted fluorescence emission peak attributed to Chl's of the proximal antenna complex (77 K). These results are interpreted in terms of a redistribution of the excitedstate energy among the pigments of the RC multimer, leading to loss of the excited state via fluorescence in the D1-L210H mutant.

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