Showing papers in "Accounts of Chemical Research in 1991"

Spin control in organic molecules

Abstract: Magnetism has fascinated and served humanity for almost 3000 years. Since the discovery of the lodestone (FeO-Fe_2O_3), many different magnetic materials have been developed, almost all based on transition metals and/or rare-earth elements. Technological application of magnetism also has a long history, from the compass to today's sophisticated magnetic memory systems. In contrast, the theory of magnetism has progressed more slowly, despite the efforts of great minds throughout history. The reason early theoretical models were not very valuable is now clear. Any viable theory of magnetism must be based on two inherently quantum mechanical concepts: electron spin and the Pauli exclusion principle. As such, only the 20th century has produced a competent model for magnetism, and that model continues to evolve. Studies over the last 20 years have revealed a bewildering array of new magnetic phenomena that continue to challenge our understanding of solid-state physics.

Molecular recognition and chemistry in restricted reaction spaces. Photophysics and photoinduced electron transfer on the surfaces of micelles, dendrimers, and DNA

Abstract: This Account is concerned with molecular recognition in bimolecular reactions1 that occur in restricted spaces. Bimolecular reactions of interest are photoinduced electron transfers for which the reactants are positively electronically excited metal complexes (Figure 1) and another positively charged gegenion, either a metal complex or methyl viologen (MV^(2+)) that serves as an electron acceptor. The restricted reaction spaces are the interfacial regions of anionically charged polyions such as micelles, starburst dendrimers, and DNA. Molecular recognition is concerned with how specific sites on a molecular receptor are recognized by a binding substrate. Knowledge of the underlying principles of molecular recognition is useful in diverse activities such as the design of site- and conformation-specific reagents for biomolecules, the rational design of drugs and probes of polymer structure, the design of efficient catalytic systems, the design of strategies leading to the synthesis of new materials, and the design of novel nanoscopic devices.