BODIPY dyes have attracted considerable attention as potential photosensitizers in dye‐sensitized solar cells (DSSCs) owing to their excellent optical properties and facile structural modification. This account focuses on recent advances in the molecular design of D‐π‐A BODIPY dyes for applications in DSSCs. Special attention has been paid to the structure‐property relationships of D‐π‐A BODIPY dyes for DSSCs. The developmental process in the modified position at the BODIPY core with a donor/acceptor is described. The devices based on 2,6‐modified BODIPY dyes exhibit better photovoltaic performance over other modified BODIPY dyes. Meanwhile, the research reveals the correlation of molecular structures (various donor chromophores, extended units, molecular frameworks, and long alkyl groups) with their photophysical and electrochemical properties and relates it to their performance in DSSCs. The structure‐property relationships give valuable information and guidelines for designing new D‐π‐A BODIPY dyes for DSSCs.
This article describes recent developments in C3‐symmetric tris‐urea low‐molecular‐weight gelators and their applications. The C3‐symmetric tris‐ureas are excellent frameworks to form supramolecular polymers through noncovalent interactions. In organic solvents, hydrophobic tris‐ureas form supramolecular gels. Amphiphilic tris‐ureas form supramolecular gels in aqueous media. Functional supramolecular gels were prepared by introducing appropriate functional groups into the outer sphere of tris‐ureas. Supramolecular hydrogels obtained from amphiphilic tris‐ureas were used in the electrophoresis of proteins. These electrophoreses results showed several unique characteristics compared to typical electrophoreses results obtained using polyacrylamide matrices.
Supramolecular drug delivery systems (SDDSs), including various kinds of nanostructures that are assembled by reversible noncovalent interactions, have attracted considerable attention as ideal drug carriers owing to their fascinating ability to undergo dynamic switching of structure, morphology, and function in response to various external stimuli, which provides a flexible and robust platform for designing and developing functional and smart supramolecular nano‐drug carriers. Pillar[n]arenes represent a new generation of macrocyclic hosts, which have unique structures and excellent properties in host–guest chemistry. This account describes recent progress in our group to develop pillararene‐based stimuli‐responsive supramolecular nanostructures constructed by reversible host–guest interactions for controllable anticancer drug delivery. The potential applications of these supramolecular drug carriers in cancer treatment and the fundamental questions facing SDDSs are also discussed.
A large variety of synthetic methods have been developed for the synthesis of functionalized aliphatic amines because of their broad spectrum of application. Metallic reagents/catalysts and/or toxic oxidants are involved in most of the cases. Direct C? H functionalization of aliphatic amines via their classical condensation reactions with suitable carbonyl compounds is advantageous because this method avoids hazardous metallic reagents, toxic oxidants and pre‐activation/pre‐functionalization step(s). In this account, the concept of direct C? H functionalization of aliphatic amines based on the classical condensation–isomerization–addition (CIA) strategy followed by recent contributions from our ongoing research in the field along with relevant examples from other groups are described. Successes in stereo‐ and regioselective C? C and C? O bond formation via direct α‐ as well as β‐C(sp3)–H functionalization are discussed.
Push–pull molecules represent a unique and fascinating class of organic π‐conjugated materials. Herein, we provide a summary of their recent extraordinary design inspired by letters of the alphabet, especially focusing on H‐, L‐, T‐, V‐, X‐, and Y‐shaped molecules. Representative structures from each class were presented and their fundamental properties and prospective applications were discussed. In particular, emphasis is given to molecules recently prepared in our laboratory with T‐, X‐, and Y‐shaped arrangements based on indan‐1,3‐dione, benzene, pyridine, pyrazine, imidazole, and triphenylamine. These push–pull molecules turned out to be very efficient charge‐transfer chromophores with tunable properties suitable for second‐order nonlinear optics, two‐photon absorption, reversible pH‐induced and photochromic switching, photocatalysis, and intercalation.
A series of N‐sulfinyl dienophiles 1c‐i has been screened in asymmetric hetero‐Diels‐Alder reactions using chiral bis(oxazoline)copper(II) and ‐zinc(II) triflates. The survey pointed out N‐sulfine 1c (R ? P(?O)(OPh)2) as the most promising N‐sulfine regarding yield and stereoselectivity (up to 97% ee). The relative configurations, and in one case the absolute configuration, of the HDA adducts were established by X‐ray analysis. 相似文献
The direct functionalization of C(sp3)–H bonds is one of the most synthetically powerful research areas in current organic synthesis. Organocatalytic C(sp3)–H bond activation reactions have recently been developed in addition to the traditional metal‐catalyzed C(sp3)–H activation reactions. In this review, we aim to give a brief overview of organo‐ and organometallic internal redox cascade reactions with respect to the mechanism, the reactivity of hydrogen donors and acceptors, and the migration modes of hydrogen.
The direct addition of Csp2–H bonds onto polar C=C, C=O, and C=N bonds is both synthetically and mechanistically important, because using aromatic C–H substrates in place of organometallic reagents provides a more direct and atom‐economical alternative to many important compounds without the pre‐generation of organometallic compounds from stoichiometric halides and the unavoidable generation of stoichiometric metal halide waste. In this account, we summarize our contributions to the transition‐metal‐catalyzed addition of aromatic C–H bonds to polar C=C, C=O, and C=N bonds via directing‐group‐assisted regiospecific reactions. These synthetic methods provide efficient access to benzylic alcohols, alkylbenzenes, 3‐substituted phthalides, N‐substituted phthalimides, N‐aryl benzamides, and indene derivatives from commercially available reagents. It is worth noting that valuable heterocycles such as 3‐substituted phthalides and N‐substituted phthalimides can be obtained in one step by this approach.
Ever since the first example of a double‐decker complex (SnPc2) was discovered in 1936, MPc2 complexes with π systems and chemical and physical stabilities have been used as components in molecular electronic devices. More recently, in 2003, TbPc2 complexes were shown to be single‐molecule magnets (SMMs), and researchers have utilized their quantum tunneling of the magnetization (QTM) and magnetic relaxation behavior in spintronic devices. Herein, recent developments in LnIII‐Pc‐based multiple‐decker SMMs on surfaces for molecular spintronic devices are presented. In this account, we discuss how dinuclear TbIII‐Pc multiple‐decker complexes can be used to elucidate the relationship between magnetic dipole interactions and SMM properties, because these complexes contain two TbPc2 units in one molecule and their intramolecular TbIII?TbIII distances can be controlled by changing the number of stacks. Next, we focus on the switching of the Kondo signal of TbIII‐Pc‐based multiple‐decker SMMs that are adsorbed onto surfaces, their characterization using STM and STS, and the relationship between the molecular structure, the electronic structure, and the Kondo resonance of TbIII‐Pc multiple‐decker complexes.
Ligand functionalization in metal–organic frameworks (MOFs) has been studied extensively and has been demonstrated to enhance gas adsorption and induce interesting gas adsorption phenomena. This account summarizes our recent study of three series of MOFs by ligand functionalization, as well as their carbon dioxide adsorption properties. While ligand functionalization does not change the overall structure of the frameworks, it can influence their gas adsorption behavior. In the first two series, we show how ligand functionalization influences the CO2 affinity and adsorption capacity of MOFs. We also show a special case in which subtle changes in ligand functionality alter the CO2 adsorption profile.
A linear supramolecular polymer based on the self‐assembly of an easily available copillar[5]arene monomer is efficiently prepared, which is evidenced by the NMR spectroscopy, viscosity measurement, and DOSY experiment. The single‐crystal X‐ray analysis reveals that the polymerization of the AB‐type monomer is driven by the quadruple CH•••π interactions and one CH•••O interaction.
Regio‐ and stereoselective 1,3‐dipolar cycloaddition of nitrile oxides to internal 2‐pentenols and α,β‐unsaturated esters catalyzed by (?) sparteine‐lanthanide complexes affords corresponding 3‐aryl‐2‐isoxazolines with enantioselectivities up to 68% ee. 相似文献
Coordination polymers serving as molecular magnetic refrigerants have been attracting great interest. In particular, coordination cluster compounds that demonstrate their apparent advantages on cryogenic magnetic refrigerants have attracted more attention in the last five years. Herein, we mainly focus on depicting aspects of syntheses, structures, and magnetothermal properties of coordination clusters that serve as magnetic refrigerants on account of the magnetocaloric effect. The documented molecular magnetic refrigerants are classified into two primary categories according to the types of metal centers, namely, homo‐ and heterometallic clusters. Every section is further divided into several subgroups based on the metal nuclearity and their dimensionalities, including discrete molecular clusters and those with extended structures constructed from molecular clusters. The objective is to present a rough overview of recent progress in coordination‐cluster‐based molecular magnetic refrigerants and provide a tutorial for researchers who are interested in the field.
Pillararene‐containing thermoresponsive polymers are synthesized via reversible addition–fragmentation chain transfer polymerization using pillararene derivatives as the effective chain transfer agents for the first time. These polymers can self‐assemble into micelles and form vesicles after guest molecules are added. Furthermore, such functional polymers can be further applied to prepare hybrid gold nanoparticles, which integrate the thermoresponsivity of polymers and molecular recognition of pillararenes.
Transition‐metal complex triplet photosensitizers are versatile compounds that have been widely used in photocatalysis, photovoltaics, photodynamic therapy (PDT) and triplet–triplet annihilation (TTA) upconversion. The principal photophysical processes in these applications are the intermolecular energy transfer or electron transfer. One of the major challenges facing these triplet photosensitizers is the short triplet‐state lifetime, which is detrimental to the above‐mentioned photophysical processes. In order to address this challenge, transition‐metal complexes showing long‐lived triplet excited states are highly desired. This review article summarizes the development of this fascinating area, including the molecular design rationales, the principal photophysical properties, and the applications of these complexes in PDT and TTA upconversion.
We present herein a personal account of our achievements in the development of novel catalytic systems based on late‐transition‐metal complexes for the hydroarylation of alkynes. In particular, our targets were intermolecular hydroarylation reactions with arene or heteroarene substrates devoid of directing groups. We have shown that complexes of palladium, platinum or gold with N‐heterocyclic carbene (NHC) ligands can be particularly useful catalysts for this reaction; the NHC ligand imparts greater stability to the complex and renders the catalytic system more productive. Furthermore, we have identified promoters and reaction media that allow to significantly improve the catalytic activity under mild conditions, to control the reaction chemoselectivity and to steer it towards more complex products; thus making this reaction considerably more attractive for the synthetic chemist.
For efficient photoresponses of liquid‐crystal (LC) azobenzene (Az) polymer systems, planar LC orientation of the Az mesogenic group is required because the light irradiation process usually occurs with normal incidence to the film surface. However, LC molecules with a rodlike shape tend to orient perpendicularly to the film surface according to the excluded volume effect theory. This review introduces new approaches for inducing planar orientation in side‐chain LC Az polymer films via interface and surface molecular designs. The planar orientation offers efficient in‐plane photoalignment and photoswitching to hierarchical LC architectures from molecular LC mesogens and LC phases to mesoscopic microphase‐separated structures. These approaches are expected to provide new concepts and possibilities in new LC polymer devices.
Asymmetric hydrogenation is one of the most efficient and atom‐economical tools to prepare chiral molecules. However, the enantiodiscrimination of simple, minimally functionalized olefins is still challenging and requires more sophisticated ligand design. Herein, we discuss our progress in the successful development of ligand design for the iridium‐catalyzed asymmetric hydrogenation of minimally functionalized olefins.
Aggregation‐induced emission (AIE) luminogens show abnormal fluorescent behavior; they are non‐emissive in solution, but they become strongly emissive after aggregation. Sensing and imaging are the major applications of AIE luminogens. By properly manipulating the aggregation and deaggregation of AIE molecules, various bio‐/chemosensors have been developed. Moreover, AIE molecules with targeting groups have been devised for imaging of organelles and cancer cells. In this account, we report our recent work on the application of AIE luminogens for the construction of bio‐/chemosensors and imaging.
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