Synthetic expanded porphyrin chemistry

Expanded porphyrins are synthetic analogues of the porphyrins, and differ from these and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core with a minimum of 17 atoms, while retaining the extended conjugation features that are a hallmark of these quintessential biological pigments. The result of core expansion is to produce systems with novel spectral and electronic features, interesting and, often unprecedented, cation-coordination properties, and, in many cases, an ability to bind anions in certain protonation states. Also adding to the appeal of expanded porphyrins is their central role in addressing issues of aromaticity. In many cases, they also display structural features, such as decidedly nonplanar "figure-eight" motifs, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. In this Review, the various synthetic approaches now being employed to produce expanded porphyrins as well as their various applications-related aspects are discussed.     

Merging porphyrins with organometallics: synthesis and applications

The coordination chemistry of porphyrins has traditionally involved the ability of the porphyrin's tetrapyrrolic core to accommodate metal ions of varying charges and sizes, and on the organometallic chemistry of the resulting metalloporphyrins. However, the organometallic chemistry of porphyrins is not necessarily restricted to the metal bound in the porphyrin core, but can also be extended to the porphyrin periphery, be it through direct metalation of the porphyrin macrocycle at the meso or beta position, or by attachment to or merger of the porphyrin skeleton with ligands, followed by metalation. This Review focuses on the synthetic strategies used for porphyrins with peripheral metal-carbon bonds. The exciting results that have been produced underscore the importance and future potential of this field.     

Enzyme mimics based upon supramolecular coordination chemistry

Recent advances in supramolecular coordination chemistry have allowed chemists to synthesize macromolecular complexes that exhibit various properties intrinsic to enzymes. This Review focuses on structures inspired by properties and functions observed in enzymes rather than precise models of enzyme active sites. These structures are synthesized using convergent, modular, and high-yielding coordination-chemistry-based methods, which allow one to tailor the size, shape, and properties of the resulting complexes. Many of the structures discussed exhibit reactivity and specificity reminiscent of natural systems, and some of them have functions that exceed the natural systems which provided the inspiration for initially making them.     

Hexaphyrin–Cyclodextrin Hybrids: A Nest for Switchable Aromaticity,Asymmetric Confinement,and Isomorphic Fluxionality

Conformational control over the highly flexible π‐conjugated system of expanded porphyrins is a key step toward the fundamental understanding of aromaticity and for the development of molecular electronics. We have synthesized unprecedented hexaphyrin–cyclodextrin (HCD) capped hybrids in which the hexaphyrin part is constrained in a planar rectangular conformation in either a 26 or a 28 π‐electron oxidation state ( [26] / [28]HCD ). These structures display strong aromaticity and antiaromaticity, respectively, exhibit markedly different chiroptical properties, and are interconvertible upon the addition of DDQ or NaBH(OAc)₃, thus affording a rare switchable aromatic–antiaromatic system with a free‐base expanded porphyrin. Conformational analysis revealed discrimination of the two coordination sites of the hexaphyrin, one of which was coupled to a confined asymmetric environment, and fluxional behavior consisting of apparent rotation of the hexaphyrin cap through a shape‐shifting mechanism.     

Hexaphyrin–Cyclodextrin Hybrids: A Nest for Switchable Aromaticity,Asymmetric Confinement,and Isomorphic Fluxionality

Conformational control over the highly flexible π‐conjugated system of expanded porphyrins is a key step toward the fundamental understanding of aromaticity and for the development of molecular electronics. We have synthesized unprecedented hexaphyrin–cyclodextrin (HCD) capped hybrids in which the hexaphyrin part is constrained in a planar rectangular conformation in either a 26 or a 28 π‐electron oxidation state ( [26] / [28]HCD ). These structures display strong aromaticity and antiaromaticity, respectively, exhibit markedly different chiroptical properties, and are interconvertible upon the addition of DDQ or NaBH(OAc)₃, thus affording a rare switchable aromatic–antiaromatic system with a free‐base expanded porphyrin. Conformational analysis revealed discrimination of the two coordination sites of the hexaphyrin, one of which was coupled to a confined asymmetric environment, and fluxional behavior consisting of apparent rotation of the hexaphyrin cap through a shape‐shifting mechanism.     

Organometallic Ionic Liquids Containing Sandwich Complexes: Molecular Design,Physical Properties,and Chemical Reactivities

Ionic liquids (ILs) are salts with low melting points and are useful as electrolytes and solvents. We have developed ILs containing cationic metal complexes, which form a family of functional liquids that exhibit unique physical properties and chemical reactivities originating from metal complexes. Our study explores the liquid chemistry in the field of coordination chemistry, where solid-state chemistry is currently the main focus. This review describes the molecular design, physical properties, and reactivities of organometallic ILs containing sandwich or half-sandwich complexes. This paper mainly covers stimuli-responsive ILs, whose magnetic properties, solvent polarities, colors, or structures change by the application of external fields, such as light, heat, and magnetic fields, or by reaction with coordinating molecules.     

卟啉衍生物的合成与性能研究进展

卟啉化学是有机化学研究中不可或缺的一个方向。由于卟啉在结构上具有一个大的共轭体系,从而具有典型的芳香性。其具有优异的光电性能、独特的光动力治疗作用、高效的催化活性,并且广泛存在于血红素、叶绿素、维生素B_(12)、过氧化氢酶等有机生物分子中,所有这一切都吸引着科学家们进行深入研究。本文从取代卟啉、缩合卟啉以及扩环卟啉三个方面分别讨论了卟啉的研究进展,通过列举一系列经典的反应以及卟啉衍生物,总结了卟啉衍生物的合成方法及其发展方向。另外,文中还对于卟啉的一些特殊物理、化学和光电性质,做了重点介绍。本文旨在为卟啉的研究者们提供参考。     

Boron complexes of porphyrins and related polypyrrole ligands: unexpected chemistry for both boron and the porphyrin

The coordination of boron to a range of polypyrrole-containing ligands is explored in this feature article. The boron dipyrromethenes are well-known as laser dyes and fluorescent labels in biology. Subphthalocyanine and subporphyrin macrocycles containing only three pyrrole rings can exist only when templated by a central boron atom. Boron complexes of expanded porphyrins (six or eight pyrroles) can complex boron in dipyrromethene (but not bipyrrole) sites. The primary focus of the article is on boron porphyrin and corrole complexes, where the tight fit of two boron atoms within the very constrained coordination site gives rise to unexpected chemistry at both boron and the porphyrin ligand. These unusual features are described and reasons for their occurrence postulated.     

Photoinduced Electron Transfer of Porphyrin Isomers: Impact of Molecular Structures on Electron‐Transfer Dynamics

Porphyrins have been investigated for a long time in various fields of chemistry owing to their excellent redox and optical properties. Structural isomers of porphyrins have been synthesized, namely, porphycene, hemiporphycene, and corrphycene. Although the number of studies on these structural isomers is limited, they exhibit interesting properties suitable for various applications such as photovoltaic devices, photocatalysts, and photodynamic therapy. In the present review, we summarized their photoinduced electron‐transfer processes, which are key steps of various photofunctions. Their electrochemical and photophysical properties are summarized as basic properties for the electron transfer. Furthermore, differences among these isomers in the electron‐transfer processes are clarified, and its origin has been discussed on the basis of their molecular structures.     

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

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.     

The coordination of bismuth by porphyrins

The coordination chemistry of porphyrins towards the complexation of bimuth(III) has been investigated. Although the insertion of bismuth is tedious in porphyrins such as octa-ethyl porphyrin (OEP) or tetra-tolyl porphyrin (TTP), we have demonstrated that simple modifications of the ligand, like the grafting of arms bearing either ester groups or acid functions, lead to stable complexes, resulting from a rapid complexation reaction.     

微孔配位聚合物作为新型储氢材料的研究

微孔配位聚合物性质独特、结构多样,具有广泛的应用前景,它已成为近几年来一个热门的研究领域。本文简要介绍该类化合物作为一种新型的储氢材料,在合成、结构和储氢性能方面的研究进展。     

Open-framework structures of transition-metal compounds

Inorganic framework solids are no longer limited to just the silicates and phosphates. Recent research has revealed that carboxylates, arsenates, sulfates, selenates, selenites, germanates, phosphites can also form such structures. One of the emerging areas combines the rich coordination chemistry of the central metal ions of many of these structures with the flexibility and functionality of the organic linkers to give rise to organic-inorganic hybrid compounds. The compounds of the transition-metals appear to provide many variations arising from their coordination preferences, ligand geometry, and the valence state. In addition, the combination of the magnetic nature of the transition metal center with the channel structure of open frameworks suggests interesting potential applications. In this Review the synthesis, structures and properties of the various transition-metal open-framework compounds are discussed.     

Photophysical properties of core-modified expanded porphyrins: nature of aromaticity and enhancement of ring planarity

We have investigated the excited-state dynamics and nonlinear optical properties of representative core-modified expanded porphyrins, tetrathiarubyrin, tetraselenarubyrin, pentathiaheptaphyrin, tetrathiaoctaphyrin, and tetraselenaoctaphyrin, containing 26, 30, and 34 pi electrons using steady-state and time-resolved absorption and fluorescence spectroscopic measurements along with femtosecond Z-scan method, with a particular attention to the photophysical properties related to molecular planarity and aromaticity. Core-modification of macrocycles by sulfur and selenium leads to NIR-extended steady-state absorption and fluorescence spectra and short-lived excited-state due to the heavy-atom effect in time-resolved spectroscopic experiments. Large negative nucleus-independent chemical shift values ranging from -13 to -15 ppm indicate that all molecular systems are highly aromatic. The observed enhancement of two-photon absorption cross-section values over 10 (4) GM for core-modified hepta- and octaphyrins is mainly attributable to their rigid and planar structures as well as their aromaticity. Overall, the observed spectroscopic and theoretical results consistently demonstrate the enhanced molecular planarity of core-modified expanded porphyrins compared with their corresponding all-aza expanded porphyrins.     

Chiral Ligand-Driven Systematic Synthesis of Coordination Polymers with Non-centrosymmetric Structures

Chirality is an important concept in chemistry revealing intriguing optical properties such as circular dichroism (CD), circularly polarized luminescence (CPL), etc. As one of the non-centrosymmetric (NCS) classes, chiral materials with extended structures may exhibit unique nonlinear optical (NLO) properties, such as second-harmonic generation (SHG). In this Concept article, a series of recently discovered NCS coordination polymers (CPs) from use of carefully designed chiral organic ligands are reviewed. Combining several metal cations such as lanthanides, lead, zinc, and cadmium with rigid chiral ligands has resulted in interesting CPs with both polar and nonpolar structures. Detailed structures, SHG properties, and structure-property relationships are provided. The importance of hyperpolarizability formed by intermolecular hydrogen boding interactions to SHG is emphasized.     

The Coordination Chemistry of f-Block Elements in Molten Salts

The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties.     

Porphyrin complexes of the period 6 main group and late transition metals

Metalloporphyrin complexes of the period six metals gold, mercury, thallium, lead and bismuth are often overlooked in favour of their lighter congeners. These complexes exhibit unusual coordination geometries, prominently featuring the metal centre residing out the porphyrin plane. Not only are these compounds chemically interesting, but several applications for these complexes are beginning to emerge. Gold and bismuth porphyrins have medicinal applications including novel chemotherapeutics and sensitizers for α-radiotherapy, while gold porphyrins have applications in materials chemistry and catalysis. This perspective serves to highlight trends in the synthesis and structure of these heavy metal complexes as well as illustrate the considerations necessary for rationally designing elaborate porphyrin architectures.     

Zintl ions, cage compounds, and intermetalloid clusters of Group 14 and Group 15 elements

For a long time, Zintl ions of Group 14 and 15 elements were considered to be remarkable species domiciled in solid-state chemistry that have unexpected stoichiometries and fascinating structures, but were of limited relevance. The revival of Zintl ions was heralded by the observation that these species, preformed in solid-state Zintl phases, can be extracted from the lattice of the solids and dissolved in appropriate solvents, and thus become available as reactants and building blocks in solution chemistry. The recent upsurge of research activity in this fast-growing field has now provided a rich plethora of new compounds, for example by substitution of these Zintl ions with organic groups and organometallic fragments, by oxidative coupling reactions leading to dimers, oligomers, or polymers, or by the inclusion of metal atoms under formation of endohedral cluster species and intermetalloid compounds; some of these species have good prospects in applications in materials science. This Review presents the enormous progress that has been made in Zintl ion chemistry with an emphasis on syntheses, properties, structures, and theoretical treatments.     

Boron complexes of pyrrolyl ligands

Complexes of boron with ligands containing pyrrolyl motifs are surveyed. The ligands range from simple pyrrolyl groups to dipyrroles and linear terpyrroles. Macrocyclic ligands include tripyrroles, which encompass subphthalocyanines, subporphyrins, subtriazaporphyrins, and subtribenzoporphyins, the familiar tetrapyrroles porphyrin and corrole but also N-confused and -fused porphyrins, and expanded porphyrins containing up to eight pyrroles. The role of boron in these compounds depends on the nature of the ligand. Boron acts as a Lewis acid center in simple boron pyrrolyl compounds, and as a structure-directing and templating agent in the cyclic terpyrroles and some of the expanded porphyrins. The difluorboron dipyrrins are well-known as fluorescent dyes. Boron porphyrins and corroles are unusual in containing two coordinated boron atoms rather than the single coordinated atom usually occurring in these ligands, and the proximity of two boron atoms at close quarters in the ligand cavities gives rise to some unusual reaction and redox chemistry. The survey is organized by the number of pyrrole moieties occurring in the ligand and focuses on new and unique chemistry observed for the complexes.     

Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipolarizabilities, and they may be ascribed as the "mixture" of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic х (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.