CONTENTS 1. Introduction 962 1.1. Prologue 962 1.2. Parent Perylene Bisimide Chromophore 963 1.3. Core-Substituted Perylene Bisimides 964 1.4. Perylene Bisimides in the Solid State 966 1.5. Areas of Application 966 2. Linear, Dendritic, and Macrocyclic Covalent PBI Ensembles 968 2.1. Excitonic Coupling and Deactivation Processes of Photoexcited PBIs 969 2.2. Rigid PBI Dimers 971 2.3. Flexible PBI Ensembles 974 2.4. Cyclic PBI Ensembles 976 3. π-Stacked PBI Assemblies 979 3.1. Self-Assembly of Core-Unsubstituted PBIs in Solution 979 3.2. Organization of Core-Unsubstituted PBIs in the Bulk Solid State 984 3.3. Self-Assembly of Amphiphilic PBIs in Aqueous Media and Solid Bulk State 987 3.4. Self-Assembly of Core-Substituted PBIs 991 3.5. Self-Assembly of Dye Arrays Composed of Multiple PBIs 995 3.6. Self-Assembly of Multichromophoric PBI Conjugates Containing Other Dyes 996 4. Hydrogen-Bond Directed Self-Assembly 1000 4.1. Self-Assembly Directed by Imide−Imide H-Bonding Interactions 1000 4.2. Self-Assembly Directed by Side-Chain Amide−Amide H-Bonding Interactions 1003 4.3. Self-Assembly Directed by Other H-Bonding Interactions 1006 4.4. Coassembly Directed by Imide−Melamine H-Bonding Interactions 1008 4.5. Coassembly Directed by Melamine−Cyanurate/Barbiturate H-Bonding Interactions 1011

No abstract

A density functional theory (DFT) database of 66 Pt(111)/O formation energies is presented. We fit this database of formation energies to a range of cluster expansions (CEs) of systematically increasing size and flexibility. We find that the performance of the CE depends upon the property or properties of interest. Pair-wise CEs with up to third nearest neighbor interactions poorly predict all metrics. CEs with five to eight pairwise interactions and one to two triplet interactions predicted formation energies and most ground states accurately but predicted average and differential adsorption energies with modest errors. A larger CE captures average and differential adsorption energies as well as formation energies and ground states. The choice of figures in the CEs is also examined. Pair-wise figures and the linear, 1-1-3, triplet are necessary to obtain CEs that qualitatively reproduce the examined properties; however, other figures are more interchangeable. The electronic and strain components of the adsorbate-adsorbate interactions is studied by comparing a CE of DFT formation energies in which atoms were not allowed to relax to the CEs of the relaxed surface. On an unrelaxed Pt surface, interactions are shorter-ranged interactions and more repulsive at first nearest neighbor separation.

The reduction of a highly electron deficient PBI afforded the corresponding dianion disodium salt that was characterized by single crystal structure analysis.

Exciton coupling is of fundamental importance and determines functional properties of organic dyes in (opto-)electronic and photovoltaic devices. Here we show that strong exciton coupling is not limited to the situation of equal chromophores as often assumed. Quadruple dye stacks were obtained from two bis(merocyanine) dyes with same or different chromophores, respectively, which dimerize in less-polar solvents resulting in the respective homo- and heteroaggregates. The structures of the quadruple dye stacks were assigned by NMR techniques and unambiguously confirmed by single-crystal X-ray analysis. The heteroaggregate stack formed from the bis(merocyanine) bearing two different chromophores exhibits remarkably different ultraviolet/vis absorption bands compared with those of the homoaggregate of the bis(merocyanine) comprising two identical chromophores. Quantum chemical analysis based on an extension of Kasha's exciton theory appropriately describes the absorption properties of both types of stacks revealing strong exciton coupling also between different chromophores within the heteroaggregate.

Well-defined hydrogen-bonded water networks inside differently sized ruthenium macrocycles facilitate cooperative proton-coupled electron transfers, and accelerate the water oxidation catalysis.

No abstract

Cluster-expansion-based kinetic model reveals that adsorbate interactions both promote and inhibit NO oxidation on the late transition metals.