STUDIES ON MECHANIS OF PHOTOSENSITIZED ISOMERIZATION OF NORBORNADIENE DERIVATIVES

Using acridine dyes as sensitizers,the photoisomerization of three norbornadiene derivatives was investigated.The valence isomerization of nor- bornadiene derivatives(Ⅰ_a,Ⅰ_b,Ⅰ_c)gave their corresponding isomers of quadri- cyclane(Ⅱ_a,Ⅱ_b,Ⅱ_c)operating with relatively high efficiency in an electron transfer mode.Their quantum yields of isomerization were determined and the reaction mechanism was discussed.

ELECTRON TRANSFER AND PHOTOCHEMICAL VALENCE ISOMERIZATION IN ANTHRACENE AND NORBORNADIENE SYSTEMS

To harvest the sun light and to promote the amount of energy stored,a new binary compound which links a sensitizer(electron donor), anthracene,and substrate(electron acceptor),norbornadiene,in a non- conjugated manner without increase in molecular weight was synthesized.The inter-and intramolecular photosensitized isomerization and the mechanism were studied.

Oxidation of norbornadiene:Theoretical investigation on H-atom abstraction and related radical decomposition reactions

The chemical kinetics of hydrogen atom(H-atom)abstraction reactions from norbornadiene(NBD)by five radicals(H,O(^(3)P),OH,CH_(3),and HO_(2)),and the unimolecular reactions of three NBD derived radicals,were studied through high-level ab-initio calculations.The geometries optimization and vibrational frequencies calculation for all the reactants,transition states,and products were obtained at the M06-2X/6-311ttG(d,p)level of theory.The zeropoint energy(ZPE)corrected potential energy surfaces(PESs)were determined at the QCISD(T)/cc-pVDZ,TZ level of theory with basis set corrections from MP2/cc-pVDZ,TZ,QZ methods for single point energy calculations.Conventional transition state theory(TST)was used for the rate constants calculations of H-atom abstraction reactions by five radicals(H,O(^(3)P),OH,CH_(3),and HO_(2))at temperatures from 298.15 to 2000 K,while the a-site H-atom abstraction reaction rate constant of NBD by OH radical has been obtained through variational transition state theory(VTST).The results show that the H-atom abstraction reactions from the α-carbon atom of NBD are the most critical channels at low temperatures.Total rate constants for H-atom abstraction reactions by OH radical are also the fastest among all of the reaction channels investigated at the temperature range from 298.15 to 2000 K.Rice-Ramsperger-Kassel-Marcus/Master Equation(RRKM/ME)has been used to calculate the pressure-and temperature-dependent rate constants for the unimolecular reactions of three related C7H7 product radicals which generated from H-atom abstraction reaction within temperature ranges of 300-2000 K and pressures of 0.01-100 atm.A combination of composite methods has been used to calculate the temperature-dependent thermochemical properties of NBD and related radicals.All the calculated kinetics and thermochemistry data can be utilized in the model development for NBD oxidation.

Photoisomerization of norbornadiene group in a rigid bichromophoric compound initiated by remote keto chromophore: long-distance through-bond triplet energy transfer

A diad compound 3 beta(bicyclo[2,2,1]hepta-2,5-diene-2-methylcarboxylate-3-carboxy)-androst-5-en-17-one (NBD-S-ONE) was synthesized and its photochemistry was examined. Irradiation of NBD-S-ONE in acetonitrile at lambda > 300 nm selectively excited the keto chromophore. After intersystem crossing, the triplet energy of the keto group was transferred to the NBD group with 18.6% efficiency via a through-bond mechanism, resulting in the isomerization of the latter group to the quadricyclane group.

Photoluminescence quenching of quantum-confined cadmium sulfide clusters by norbornadiene derivatives

Influence of norbornadiene and its derivatives on the photoluminescence (PL) of quantum-confined cadmium sulfide clusters (Q-CdS) prepared in reverse micelles wm investigated. It was found that norbornadiene-2,3-dicarboxylic acid (3) and its monopotassium salt (4) quenched PL intensity by 77% and 62%, respectively, whereas its dipotassium salt (a), norbornadiene (1) and norbornadiene-2,3-dimethylcarboxylate (2) had no effect on PL intensity. The formation constants for adducts formed between defect sites at the surface of Q-CdS clusters and 3 or 4 were also determined. PL quenching effect was attributed to the presence of ionizable proton which is considered to be able to trap photogenerated electrons and remove them from possible decay process. Measurements of the PL decay by single photon counting technique also supported these steady-state observations.