The electrochemistry and electrogenerated chemiluminescence (ECL) of two ter(9,9-diarylfluorene)s, TDAFs, were investigated. The ECL from these new blue emitters produced by ion annihilation showed spectra with significant emission at longer wavelengths and was different from their fluorescence spectra. This was ascribed to the formation of excimers. Excimer emission was not observed in ECL during the reduction of the TDAFs with benzoyl peroxide (BPO) as a coreactant, where the ECL spectra were essentially the same as their fluorescence spectra, consistent with the requirement of ion annihilation for excimer production. Excimer emission is not seen in fluorescence, even at relatively high concentrations, because of the short lifetime of 1 TDAF*. The quantum yields, φ ECL , for the ECL by ion annihilation were 0.05% for TDAF-1 and 0.01% for TDAF-2. ECL with BPO as a coreactant produced 8% (TDAF-1) or 3% (TDAF-2) of the ECL intensity of Ru(bpy) 3 2+ generated under the same conditions (0.5 mM TDAF or Ru(bpy) 3 2+ /5 mM BPO).

Noncovalently linked electron donor-acceptor complexes consisting of either zinc tetraphenylporphyrin, (TPP)Zn, or zinc octaethylporphycene, (OEPc)Zn, as donor and pyridine appended C(60), py approximately C(60), as acceptor, via axial coordination of zinc, are reported. The UV-visible and (1)H NMR spectral studies reveal 1:1 complex formation between the donor and acceptor entities. The determined K values follow the oxidation potential of the employed zinc tetrapyrroles, and the calculated thermodynamic parameters reveal stable complexation. The singlet emission studies show efficient quenching of the investigated zinc tetrapyrrole emission upon axial coordination of pyridine appended C(60). Free-energy calculations indicate that the photoinduced electron transfer from the singlet excited zinc tetrapyrrole to C(60) is exergonic, and the estimated rates of electron transfer are found to be (2.4 +/- 0.3) x 10(8) s(-)(1) for the (TPP)Zn-py approximately C(60) complex and (2.2 +/- 0.3) x 10(8) s(-)(1) for the (OEPc)Zn-py approximately C(60) complex, respectively.

Thermal decomposition of azo(bisisobutyronitrile) in a 1,2-dichlorobenzene solution of C60 gave three regioisomeric 1,x-di(2-cyano-2-propyl)-1,x-dihydro[60]fullerenes in 12, 2, and 4% yields, assigned as the 1,4-, 1,2-, and a third isomer of still uncertain structure. The 1,4- and unidentified isomers underwent three reversible reduction steps by cyclic voltammetry, and UV−vis−NIR spectra of the mono- and dianions generated electrochemically were recorded. The first two redox potentials of the 1,4-isomer were the same as those of C60, but those of the third isomer were positively shifted by 0.23 and 0.21 V from those of C60, showing that it is an electron-deficient derivative of C60.

We report a carbon-based, three-dimensional nanofluidic transport membrane that enables gated, or on/off, control of the transport of organic molecular species and metal ions using an applied electrical potential. In the absence of an applied potential, both cationic and anionic molecules freely diffuse across the membrane via a concentration gradient. However, when an electrochemical potential is applied, the transport of ions through the membrane is inhibited.