The self-assembly and self-organization of porphyrins and related macrocycles enables the bottom-up fabrication of photonic materials for fundamental studies of the photophysics of these materials and for diverse applications. This rapidly developing field encompasses a broad range of disciplines including molecular design and synthesis, materials formation and characterization, and the design and evaluation of devices. Since the self-assembly of porphyrins by electrostatic interactions in the late 1980s to the present, there has been an ever increasing degree of sophistication in the design of porphyrins that self-assemble into discrete arrays or self-organize into polymeric systems. These strategies exploit ionic interactions, hydrogen bonding, coordination chemistry, and dispersion forces to form supramolecular systems with varying degrees of hierarchical order. This review concentrates on the methods to form supramolecular porphyrinic systems by intermolecular interactions other than coordination chemistry, the characterization and properties of these photonic materials, and the prospects for using these in devices. The review is heuristically organized by the predominant intermolecular interactions used and emphasizes how the organization affects properties and potential performance in devices.

Self-Organized Porphyrinic Materials

Endohedral metallofullerenes (EMFs), a new class of hybrid molecules formed by encapsulation of metallic species inside fullerene cages, exhibit unique properties that differ distinctly from those of empty fullerenes because of the presence of metals and their hybridization effects via electron transfer. This critical review provides a balanced but not an exhaustive summary regarding almost all aspects of EMFs, including the history, the classification, current progress in the synthesis, extraction, isolation, and characterization of EMFs, as well as their physiochemical properties and applications in fields such as electronics, photovoltaics, biomedicine, and materials science. Emphasis is assigned to experimentally obtained results, especially the X-ray crystallographic characterizations of EMFs and their derivatives, rather than theoretical calculations, although the latter has indeed enhanced our knowledge of metal–cage interactions. Finally, perspectives related to future developments and challenges in the research of EMFs are proposed. (381 references)

Current status and future developments of endohedral metallofullerenes

Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters.

In this tutorial review taking X-ray crystallographically characterized compounds as a starting point a walk is taken through the electronic and structural properties of endohedral metallofullerenes After classification of the fullerenes according to the encapsulated guest, particular attention is given to identifying factors that determine the selection of a particular carbon cage network by the internal metal cluster Some of the physical rules that determine which particular fullerene cage is formed will be discussed Concepts such as charge transfer between the cage and the guest metal ions, the topology of the cage, the separations between the 12 pentagons on the fullerene surface, and the effect of entropic factors are used to rationalize the selection of a particular cage The roles of electrochemistry and vibrational spectroscopy in combination with theoretical calculations are considered in understanding the structures of the endohedral fullerenes

Endohedral metallofullerenes: a unique host–guest association

Fullerenes have the characteristic of a hollow interior, and this unique feature triggers intuitive inspiration to entrap atoms, ions or clusters inside the carbon cage in the form of endohedral fullerenes. In particular, upon entrapping an otherwise unstable metal cluster into a carbon cage, the so-called endohedral clusterfullerenes fulfil the mutual stabilization of the inner metal cluster and the outer fullerene cage with a specific isomeric structure which is often unstable as an empty fullerene. A variety of metal clusters have been reported to form endohedral clusterfullerenes, including metal nitrides, carbides, oxides, sulfides, cyanides and so on, making endohedral clusterfullerenes the most variable and intriguing branch of endohedral fullerenes. In this review article, we present an exhaustive review on all types of endohedral clusterfullerenes reported to date, including their discoveries, syntheses, separations, molecular structures and properties as well as their potential applications in versatile fields such as biomedicine, energy conversion, and so on. At the end, we present an outlook on the prospect of endohedral clusterfullerenes.

When metal clusters meet carbon cages: endohedral clusterfullerenes

The remarkably large cluster Sc4(μ3-O)2 has been obtained trapped inside an Ih-C80 cage by conducting the vaporization of graphite rods doped with copper(II) nitrate and scandium(III) oxide in an electric arc under a low pressure helium atmosphere with an added flow of air. The product has been isolated by chromatography and identified by high-resolution mass spectrometry. The structure of Sc4(μ3-O)2@Ih-C80 has been determined by X-ray crystallography on a crystal of Sc4(μ3-O)2@Ih-C80·NiII(OEP)·2(C6H6). The Sc4(μ3-O)2 unit consists of a distorted tetrahedron of scandium atoms with oxygen atoms bridging two of its faces. The Sc−Sc distances range from 2.946(7) to 3.379(7) A.

A Distorted Tetrahedral Metal Oxide Cluster inside an Icosahedral Carbon Cage. Synthesis, Isolation, and Structural Characterization of Sc4(μ3-O)2@Ih-C80

The new endohedral fullerene, Sc2(μ2-O)@Cs(6)-C82, has been isolated from the carbon soot obtained by electric arc generation of fullerenes utilizing graphite rods doped with 90% Sc2O3 and 10% Cu (w/w). Sc2(μ2-O)@Cs(6)-C82 has been characterized by single crystal X-ray diffraction, mass spectrometry, and UV/vis spectroscopy. Computational studies have shown that, among the nine isomers that follow the isolated pentagon rule (IPR) for C82, cage 6 with Cs symmetry is the most favorable to encapsulate the cluster at T > 1200 K. Sc2(μ2-O)@Cs(6)-C82 is the first example in which the relevance of the thermal and entropic contributions to the stability of the fullerene isomer has been clearly confirmed through the characterization of the X-ray crystal structure.

Sc2(μ2-O) Trapped in a Fullerene Cage: The Isolation and Structural Characterization of Sc2(μ2-O)@Cs(6)-C82 and the Relevance of the Thermal and Entropic Effects in Fullerene Isomer Selection

Metallic nitride fullerenes (MNFs) and oxometallic fullerenes (OMFs) react quickly with an array of Lewis acids. Empty-cage fullerenes are largely unreactive under conditions used in this study. The reactivity order is Sc4O2@Ih-C80 > Sc3N@C78 > Sc3N@C68 > Sc3N@D5h-C80 > Sc3N@Ih-C80. Manipulations of Lewis acids, molar ratios, and kinetic differences within the family of OMF and MNF metallofullerenes are demonstrated in a selective precipitation scheme, which can be used either alone for purifying Sc3N@Ih-C80 or combined with a final high-performance liquid chromatography pass for Sc4O2@Ih-C80, Sc3N@D5h-C80, Sc3N@C68, or Sc3N@C78. The purification process is scalable. Analysis of the experimental rate constants versus electrochemical band gap explains the order of reactivity among the OMFs and MNFs.

/pdf/selective-complexation-and-reactivity-of-metallic-nitride-1w1pmgg0in.pdf

Selective Complexation and Reactivity of Metallic Nitride and Oxometallic Fullerenes with Lewis Acids and Use as an Effective Purification Method

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A Distorted Tetrahedral Metal Oxide Cluster inside an Icosahedral Carbon Cage. Synthesis, Isolation, and Structural Characterization of Sc4(μ3-O)2@Ih-C80

Sc2(μ2-O) Trapped in a Fullerene Cage: The Isolation and Structural Characterization of Sc2(μ2-O)@Cs(6)-C82 and the Relevance of the Thermal and Entropic Effects in Fullerene Isomer Selection

Selective Complexation and Reactivity of Metallic Nitride and Oxometallic Fullerenes with Lewis Acids and Use as an Effective Purification Method