Synthesis, Photochromic and Luminescent Properties of Ammonium Salts of Spiropyrans.

New salts of photochromic indoline spiropyrans capable of reversibly responding to UV radiation were synthesized to develop light-controlled materials. Photoinduced reactions of the synthesized compounds were studied using absorption and luminescence spectroscopies, and the quantum yields of photoisomerization and other spectral and kinetic characteristics were measured. It was shown that the light sensitivity and photostability of the synthesized compounds are considerably influenced by the length of the spacer between the indole and ammonium nitrogen atoms.

Synthesis of fullerenyl-1,2,3-triazoles by reaction of fullerenyl azide with terminal acetylenes.

Fullerenyltriazoles were synthesized by the interaction of azidofullerene with terminal acetylenes, in which the heterocyclic fragment is directly attached to the fullerene core. The electrochemical studies of the synthesized triazole-containing fullerenes have proved that the potentials of the first reduction peaks are shifted to a less cathodic region compared to unmodified C60. According to theoretical calculations, synthesized fullerene C60 derivatives can be considered as promising acceptor components of organic solar cells.

Aminomethylation of Fullerene C60 with N,N',N″-Triaryl- or N,N',N″-Trihetaryl-1,3,5-perhydrotriazines in the Presence of EtMgBr and Ti(Oi-Pr)4.

A new method for the functionalization of fullerenes based on the reaction between in situ generated aryl- or hetaryl-containing 1,3,5-perhydrotriazines and EtMgBr in the presence of Ti(Oi-Pr)4 has been developed. The cleavage of the triazine ring under previously developed conditions1-6 results in the formation of aminomethylated derivatives of fullerene C60 with high yields (80-90%) and selectivity (∼90%).

How reliable are GIAO calculations of 1H and 13C NMR chemical shifts? A statistical analysis and empirical corrections at DFT (PBE/3z) level.

Reliability of calculated (1)H and (13)C NMR chemical shifts for various classes of organic compounds obtained with gauge-invariant atomic orbital (GIAO) approach has been studied at the PBE/3ζ level (as implemented in PRIRODA code) using linear regression analysis with experimental data. Empirical corrections for the calculated chemical shifts δ(H,calc) = δ(PBE/3ζ) - 0.08 ppm (RMS 0.18 ppm, MAD 0.66 ppm) and δ(C,calc) = δ(PBE/) (3) (ζ) - 6.35 ppm (RMS 3.09 ppm, MAD 9.42 ppm) have been developed using the sets of 263 and 308 experimental values for (1)H and (13)C chemical shifts, respectively. The confidence intervals of NMR chemical shifts at 95% confidence probability are δ(H,calc) ± 0.35 ppm for (1)H and δC,calc) ± 6.05 ppm for (13)C.