Inside the ball: An endohedral carbon monoxide complex of an open‐cage derivative of a [60]fullerene is prepared by insertion of CO through the opening. The incorporation of CO within the C60 cage is confirmed by mass spectrometry as well as 13C NMR and IR spectroscopic studies. The product releases CO under ambient conditions to recover a mixture of the endohedral water complex and the empty cage.

A new group of porphyrin-fullerene dyads with an azobenzene linker was synthesized, and the photochemical and photophysical properties of these materials were investigated using steady-state and time-resolved spectroscopic methods. The electrochemical properties of these compounds were also studied in detail. The synthesis involved oxidative heterocoupling of free base tris-aryl-p-aminophenyl porphyrins with a p-aminophenylacetal, followed by deprotection to give the aldehyde, and finally Prato 1,3-dipolar azomethineylide cycloaddition to C60. The corresponding Zn(II)-porphyrin (ZnP) dyads were made by treating the free base dyads with zinc acetate. The final dyads were characterized by their 1H NMR, mass, and UV-vis spectra. 3He NMR was used to determine if the products are a mixture of cis and trans stereoisomers, or a single isomer. The data are most consistent with the isolation of only a single configurational isomer, assigned to the trans (E) configuration. The ground-state UV-vis spectra are virtually a superimposition of the spectral features of the individual components, indicating there is no interaction of the fullerene (F) and porphyrin (H2P/ZnP) moieties in the ground state. This conclusion is supported by the electrochemical data. The steady-state and time-resolved fluorescence spectra indicate that the porphyrin fluorescence in the dyads is very strongly quenched at room temperature in the three solvents studied: toluene, tetrahydrofuran (THF), and benzonitrile (BzCN). The fluorescence lifetimes of the dyads in all solvents are sharply reduced compared to those of H2P and ZnP standards. In toluene, the lifetimes of the free base dyads are 600-790 ps compared to 10.1 ns for the standard, while in THF and BzCN the dyad lifetimes are less than 100 ps. For the ZnP dyads, the fluorescence lifetimes were 10-170 ps vs 2.1-2.2 ns for the ZnP references. The mechanism of the fluorescence quenching was established using time-resolved transient absorption spectroscopy. In toluene, the quenching process is singlet-singlet energy transfer (k approximately 10(11) s-1) to give C60 singlet excited states which decay with a lifetime of 1.2 ns to give very long-lived C60 triplet states. In THF and BzCN, quenching of porphyrin singlet states occurs at a similar rate, but now by electron transfer, to give charge-separated radical pair (CSRP) states, which show transient absorption spectra very similar to those reported for other H2P-C60 and ZnP-C60 dyad systems. The lifetimes of the CSRP states are in the range 145-435 ns in THF, much shorter than for related systems with amide, alkyne, silyl, and hydrogen-bonded linkers. Thus, both forward and back electron transfer is facilitated by the azobenzene linker. Nonetheless, the charge recombination is 3-4 orders of magnitude slower than charge separation, demonstrating that for these types of donor-acceptor systems back electron transfer is occurring in the Marcus inverted region.

We studied Ar, Kr, CO, and N(2) going into and out of a chemically opened fullerene, 1. We measured the equilibrium constant, K(eq), for the formation of X@1. K(eq) is particularly large for Ar, probably due to the large van der Waals attraction between the Ar atom and the fullerene cage. We measured rate constants and activation energies for the unimolecular reaction X@1-->X + 1 (X = Ar, CO, N(2)). The reactions show an unusually small pre-exponential factor, probably due to the loose binding of X inside the cage.

(3)He has been inserted into the cavity of an open-cage fullerene derivative close to room temperature, reaching an incorporation fraction of 0.1%. The rate of escape of (3)He from this fullerene was monitored by (3)He NMR to yield the activation barrier and to compare the size of the orifice to those of other open-cage fullerenes. The equilibrium constant was also measured.

The decadic extinction coefficient of the hydrated electron is reported for the absorption maximum from room temperature to 380 degrees C. The extinction coefficient is established by relating the transient absorption of the hydrated electrons in the presence of a scavenger to the concentration of stable product produced in the same experiment. Scavengers used in this report are SF(6,) N(2)O, and methyl viologen. The room temperature value is established as 22,500 M(-1) cm(-1), higher by 10-20% than values used over the last several decades. We demonstrate how previous workers arrived at a low value by incorrect choice of a radiolysis yield value. With this revision, the integrated oscillator strength, corrected by refractive index, is definitely (ca. 10%) larger than unity. This result is fully consistent with EPR and resonance Raman results which indicate mixing of the hydrated electron wave function with solvent electronic orbitals. Oscillator strength appears to be conserved vs temperature.

Pulse radiolysis experiments published several years ago (J. Phys. Chem. A, 2002, 106, 2430) raised the possibility that the carbonate radical formed from reaction of *OH radicals with either HCO(3)(-) or CO(3)(2-) might actually exist predominantly as a dimer form, for example, *(CO(3))(2)(3-). In this work we re-examine the data upon which this suggestion was based and find that the original data analysis is flawed. A major omission of the original analysis is the recombination reaction *OH + *CO(3)(-) --> HOOCO(2)(-). Upon reanalysis of the published data for sodium bicarbonate solutions and analysis of new transient absorption data we are able to establish the rate constant for this reaction up to 250 degrees C. The mechanism for the second-order self-recombination of the carbonate radical has never been convincingly demonstrated. From a combination of literature data and new transient absorption experiments in the 1-400 ms regime, we are able to show that the mechanism involves pre-equilibrium formation of a C(2)O(6)(2-) dimer, which dissociates to CO(2) and peroxymonocarbonate anion: *CO3(-)+*CO3(-)<-->C2O6(2-)-->CO2+O2COO(2-) *CO3(-) reacts with the product peroxymonocarbonate anion, producing a peroxymonocarbonate radical *O2COO(-), which can also recombine with the carbonate radical: *CO3(-)+CO4(2-)-->*CO4(-)+CO3(2-) *CO3(-)+CO4(-)-->C2O7(2-).

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Im Ball: Der endohedrale Kohlenmonoxidkomplex eines [60]Fullerenderivats mit geöffnetem Käfig wird durch Insertion von CO durch die Öffnung hergestellt. Das Vorliegen von CO im C60‐Käfig bestätigen massenspektrometrische sowie 13C‐NMR‐ und IR‐spektroskopische Untersuchungen. Unter Umgebungsbedingungen setzt das Produkt CO frei, wobei eine Mischung aus dem endohedralem Wasserkomplex und dem leerem Käfig zurückgewonnen wird.