Double-decker phthalocyanine complexes with Tb3+ or Dy3+ showed slow magnetization relaxation as a single-molecular property. The temperature ranges in which the behavior was observed were far higher than that of the transition-metal-cluster single-molecule magnets (SMMs). The significant temperature rise results from a mechanism in the relaxation process different from that in the transition-metal-cluster SMMs. The effective energy barrier for reversal of the magnetic moment is determined by the ligand field around a lanthanide ion, which gives the lowest degenerate substate a large |Jz| value and large energy separations from the rest of the substates in the ground-state multiplets.

Lanthanide Double-Decker Complexes Functioning as Magnets at the Single-Molecular Level

J-aggregates are of significant interest for organic materials conceived by supramolecular approaches. Their discovery in the 1930s represents one of the most important milestones in dye chemistry as well as the germination of supramolecular chemistry. The intriguing optical properties of J-aggregates (in particular, very narrow red-shifted absorption bands with respect to those of the monomer and their ability to delocalize and migrate excitons) as well as their prospect for applications have motivated scientists to become involved in this field, and numerous contributions have been published. This Review provides an overview on the J-aggregates of a broad variety of dyes (including cyanines, porphyrins, phthalocyanines, and perylene bisimides) created by using supramolecular construction principles, and discusses their optical and photophysical properties as well as their potential applications. Thus, this Review is intended to be of interest to the supramolecular, photochemistry, and materials science communities.

J-aggregates: from serendipitous discovery to supramolecular engineering of functional dye materials.

Role of Structural Factors in the Nonlinear Optical Properties of Phthalocyanines and Related Compounds

The field of non-fullerene organic solar cells has experienced rapid development during the past few years, mainly driven by the development of novel non-fullerene acceptors and matching donor semiconductors. However, organic solar cell material development has progressed via a trial-and-error approach with limited understanding of the materials’ structure–property relationships and the underlying device physics of non-fullerene devices. In addition, the availability of hundreds of donor and acceptor semiconductors creates an extremely large pool of possible donor–acceptor combinations, which poses a daunting challenge for rational material screening and matching. This Review describes several important conceptual aspects of the emerging non-fullerene devices by highlighting key contributions that provided fundamental insights regarding rational material design, donor–acceptor pair matching, blend morphology control and the reduced voltage losses in non-fullerene organic solar cells. We also discuss the key challenges that need to be addressed to develop more-efficient non-fullerene organic solar cells.

Material insights and challenges for non-fullerene organic solar cells based on small molecular acceptors

Photosynthesis is used by nature to convert light energy into chemical energy in some living systems. In such a process, a cascade of very efficient, short-range energy and electron transfer events between well-arranged, light-harvesting organic donor and acceptor pigments takes place within the photosynthetic reaction center, leading to the overall generation of chemical energy from sunlight with near quantum efficiency.1-8 During the past decade, a significant effort has been made by the scientific community toward the preparation of synthetic model compounds of natural photosynthetic systems able to convert light into other energy sources,9 probably fostered by the increasing concerns related to the utilization of fossils fuels for the production of electricity in terms of both availability and environmental issues. However, considering the structural complexity presented by the natural photosynthetic systems, much of the scientific effort has been devoted toward the preparation and study of structurally simpler systems, with the aim of reproducing some of the fundamental steps occurring in natural photosynthesis, one of the most important being the photoinduced charge separation (CS).10-12 Among the chromophores that have been used as molecular components in artificial photosynthetic systems, porphyrinoids, the ubiquitous molecular building blocks employed by nature in natural photosynthesis, have been the preferred and obvious choice, due to their intense optical absorption and rich redox chemistry.13-20 Within the large family of porphyrinoid systems, phthalocyanines (Pcs) enjoy a privileged position (Figure 1a). These chromophores, which have a two-dimensional 18-πelectron aromatic system isoelectronic with that of porphyrins (Pors), possess in fact unique physicochemical properties which render these macrocycles valuable building blocks in materials science.21-32 Pcs are thermally and chemically stable compounds which present an intense absorption in the red/near-infrared (IR) region of the solar spectrum with extinction coefficients (as high as 200 000 M-1 cm-1) and fluorescence quantum yields * To whom correspondence should be addressed. E-mail: tomas.torres@uam.es (T.T.); dirk.guldi@chemie.uni-erlangen.de (D.M.G.). † Universidad Autonoma de Madrid. ‡ Friedrich-Alexander-Universitat Erlangen-Nurnberg. § IMDEA-Nanociencia. Chem. Rev. 2010, 110, 6768–6816 6768

Covalent and noncovalent phthalocyanine-carbon nanostructure systems: synthesis, photoinduced electron transfer, and application to molecular photovoltaics.

A subazaporphyrin (SubAP), tert-butylated and crowned subphthalocyanines (tBSubPc and SubCRPc), a μ-oxo dimer of tert-butylated SubPc {(tBSubPc)2O}, a subnaphthalocyanine (SubNc), and monosubstituted type unsymmetrical phthalocyanine (Pc) and naphthalocyanine (Nc) analogues have been synthesized. In particular, unsymmetrical Pc's and Nc's have been prepared in moderate yields by the ring expansion reaction of structurally distorted SubPc's and SubNc's with isoindolediimine derivatives in dimethyl sulfoxide−chloronaphthalene (or chlorobenzenes or aromatic hydrocarbons such as toluene and xylene) mixtures. The compounds have been characterized by electronic absorption, magnetic circular dichroism (MCD), fluorescence emission, and nuclear magnetic resonance spectroscopy. Both the Soret bands and Q-bands shift to longer wavelength and gain intensity in the order SubAP, SubPc, and SubNc. Fluorescence quantum yields and lifetimes generally decrease with decreasing molecular symmetry. Circular dichroism and NMR ...

Synthesis, Spectroscopy, and Molecular Orbital Calculations of Subazaporphyrins, Subphthalocyanines, Subnaphthalocyanines, and Compounds Derived Therefrom by Ring Expansion1

Photoinduced electron transfer between fullerenes (C60 and C70) and phthalocyanines such as tetra-tert-butylphthalocyanine (H2TBPc) and its zinc derivative (ZnTBPc) in solution has been investigated with nanosecond laser photolysis method by observing the transient absorption bands in the visible/near-IR regions. By the predominant excitation of fullerenes with 532 nm laser light, slow rises of the transient absorption bands of phthalocyanine cation radicals and fullerene anion radicals were observed instead of the decays of the excited triplet states of fullerenes (TC60* and TC70*) in polar solvents. Electron-transfer from the phthalocyanines to TC60* or TC70* was confirmed. The quantum yield of the electron transfer via TC70* is higher than that via TC60*; ZnTBPc acts as stronger electron donor than H2TBPc. In nonpolar solvent, energy transfer from TC60* (and TC70*) to the phthalocyanines occurs predominantly as confirmed by the consecutive appearance of the triplet states of the phthalocyanines.

Photoinduced electron transfer from phthalocyanines to fullerenes (C60 and C70)

Cross polarization/magic angle spinning (CP/MAS)13C (solid state high resolution) NMR spectra were observed for chlorosomes and BChlc aggregates. Similarity of both kinds of spectra (except for some signals assignable to proteins and lipids in chlorosomes) indicates that BChlc's in chlorosomes are present just as in synthetic BChlc aggregates. Chemical shifts for C131 carbonyl and C31 hydroxylethyl carbons indicate hydrogen bonding between them. Comparison of solution and solid state13C NMR chemical shifts shows the five coordinated nature of BChlc aggregates. Some chemical shift differences were attributable to ring currents shifts. Their comparisons with calculated ring current shift values predicted structures for the aggregates. Cross polarization dynamics of the CP/MAS13C NMR signals explored dynamic and structural nature of the BChlc aggregates.

Hideo Konami

Papers

Synthesis, Spectroscopy, and Molecular Orbital Calculations of Subazaporphyrins, Subphthalocyanines, Subnaphthalocyanines, and Compounds Derived Therefrom by Ring Expansion1

Photoinduced electron transfer from phthalocyanines to fullerenes (C60 and C70)

Structures of chlorosomes and aggregated BChlc inChlorobium tepidum from solid state high resolution CP/MAS13C NMR

Inter-ring overlap integrals in dimer complexes of phthalocyanines and porphyrins

Redox potentials of a series of lanthanide-bisphthalocyanine sandwich complexes