The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

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Reticular synthesis and the design of new materials

This critical review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their ‘design’, aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the physical properties of the dense phases. (323 references)

Hybrid porous solids: past, present, future

BODIPY dyes and their derivatives: syntheses and spectroscopic properties.

In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

Organic Photoredox Catalysis

The Conservation of Orbital Symmetry

A Radical Anion Salt of 2,5‐Dimethyl‐N,N′‐dicyanoquinonediimine with Extremely High Electrical Conductivity

A general structural principle for organic compounds that have the capacity for two-stage electron transfer is based on the following reaction sequence: 



In this scheme one or both of the entities X may be replaced by Y⊖. The radical partners in these systems often have very high thermodynamic stability. The choice of the end groups X and Y, (partial) inclusion of n-systems in rings, alteration of the number of vinylene groups, and aza-substitution make many variations possible. By means of this general structural principle numerous known compounds are brought together and new redox systems are simultaneously set up. The aim of the present review is to demonstrate the broad applicability of this principle, to indicate its significance for science and industry, and to describe some reactions.

Multistage Organic Redox Systems—A General Structural Principle

The presence of diimine in solution can be shown conclusively by the stereospecific cishydrogenation of symmetrical multiple bonds. Apart from reactions which have hitherto been attributed to hydrazine, this review deals primarily with the various sources and secondary reactions of diimine.

The Chemistry of Diimine

Single and double bridged viologenes and intramolecular pimerization of their cation radicals

Ein allgemeines Strukturprinzip fur organische Verbindungen, die zur zweistufigen Elektronenubertragung befahigt sind, geht aus der folgenden Reaktionssequenz hervor: 






Dabei konnen ein oder beide X durch Y⊖ ersetzt sein. In diesen Systemen besitzt der radikalische Partner oft sehr grose thermodynamische Stabilitat. Wahl der Endgruppen X und Y, (teilweiser) Einbau des π-Systems in Ringe, Veranderung der Zahl der Vinylengruppen sowie Azasubstitution ermoglichen vielfaltige Variationen. Durch dieses allgemeine Strukturprinzip lassen sich zahlreiche bekannte Verbindungen zusammenfassen und zugleich neue Redoxsysteme entwerfen. Die vorliegende Ubersicht will seinen breiten Gultigkeitsbereich demonstrieren, auf seine Bedeutung fur Wissenschaft und Technik hinweisen und einige Reaktionen beschreiben.

Siegfried Hünig

Papers

A Radical Anion Salt of 2,5‐Dimethyl‐N,N′‐dicyanoquinonediimine with Extremely High Electrical Conductivity

Multistage Organic Redox Systems—A General Structural Principle

The Chemistry of Diimine

Single and double bridged viologenes and intramolecular pimerization of their cation radicals

Mehrstufige organische Redoxysteme — ein allgemeines Strukturprinzip