Skeletal Formation of Carbocycles with CO2: Selective Synthesis of Indolo[3,2-b]carbazoles or Cyclophanes from Indoles, CO2, and Phenylsilane.

The catalytic reactions of indoles with CO2 and phenylsilane afforded indolo[3,2-b]carbazoles, where the fused benzene ring was constructed by forming two C-H bonds and four C-C bonds with two CO2 molecules via deoxygenative conversions. Nine-membered cyclophanes made up of three indoles and three CO2 molecules were also obtained, where the cyclophane framework was constructed by forming six C-H bonds and six C-C bonds. These multicomponent cascade reactions giving completely different carbocycles were switched simply by choosing the solvent, acetonitrile or ethyl acetate.

Temperature-Induced Sign Inversion of Circularly Polarized Luminescence of Binaphthyl-Bridged Tetrathiapyrenophanes.

D2-symmetric (R)-binaphthyl-bridged pyrenophanes containing thioether bonds were synthesized. The pyrenophanes exhibited the temperature-induced sign inversion of circularly polarized luminescence (CPL) while maintaining the emission wavelength and reversibility. The Δglum value reached 0.02, and the FL quenching by heat was negligible. The sign inversion of CPL originates from the inversion of intramolecular excimer chirality associated with excitation dynamics. The two pyrenes form a kinetically trapped left-handed twist excimer at low temperatures, while they form a thermodynamically favored right-handed twist excimer at high temperatures. The thioether linkers can impart flexibility suitable for the inversion of chirality of the excimers.

Circularly polarized luminescence in molecular recognition systems: Recent achievements.

Circularly polarized luminescence (CPL) dyes are recognized to be new generation materials and have been actively developed. Molecular recognition systems provide nice approaches to novel CPL materials, such as stimuli-responsive switches and chemical sensing materials. CPL may be induced simply by mixing chiral or achiral, luminescent or nonluminescent host and guest; there are several combinations. Molecular recognition can potentially save time and effort to construct well-ordered chiral structures with noncovalent attractive interactions as compared with the multi-step synthesis of covalently bonded dyes. It is a challenging subject to engage molecular recognition events with CPL, and it is important and interesting to see how it is achieved. In fact, simple molecular recognition systems can even enable the fine adjustment of CPL performance and detailed conformational/configurational analysis of the excited state. Here we overview the recent achievements of simple host-guest complexes capable of exhibiting CPL, summarizing concisely the host/guest structures, CPL intensities, and characteristics.

Ruthenium Complexes Bearing Axially Chiral Bipyridyls: The Mismatched Diastereomer Showed Red Circularly Polarized Phosphorescence.

RutheniumII complexes bearing three axially chiral bipyridyl ligands were synthesized as a new family of chiral complex dyes, and Δ-(S)- and Λ-(S)-diastereomers were obtained. The X-ray crystal structure analyses, spectroscopy, and DFT calculations suggested that all the bipyridyls maintained chirality in both the ground and excited states, and the Δ-(S)- and Λ-(S)-isomers are the matched (more relaxed) and mismatched (more constrained) pairs, respectively. The mismatched Λ-(S)-isomer exhibited red circularly polarized phosphorescence (CPP) both in solution and in the solid state. The solution state CPP is the most intense of ruthenium complexes, while the solid state CPP is the first example of them. It is supposed that, for the Λ-(S)-isomer, the six cumulative CH/π interactions suppress further distortion in the T1 state.

Binaphthyl-Bridged Pyrenophanes: Intense Circularly Polarized Luminescence Based on a D2 Symmetry Strategy.

A series of D2 -symmetric macrocycles composed of alternately linked pyrene and binaphthyl moieties (binaphthyl-bridged pyrenophanes) have been synthesized. Among them, a pyrenophane possessing ether linkers at the 2,7-positions of the pyrenes exhibited intense circularly polarized luminescence (CPL) with a |glum | value of 0.053. This value is by far the highest for excimers and was not sensitive to temperature, solvent, or concentration. The CPL originated from a twisting pyrene excimer, with the (R)-binaphthyl moieties producing a left-handed twist excimer, which exhibited (-)-CPL. The electric and magnetic transition dipole moments are perfectly parallel, which is the best relationship for strong CPL.

Circularly Polarized Luminescence Liquids Based on Siloxybinaphthyls: Best Binaphthyl Dihedral Angle in the Excited State.

A series of axially chiral 1,1'-binaphthyls with trialkylsiloxy (OSiR3 ) groups were synthesized. Among them, 1 a-c possessing OSiR3 groups at the 7,7'-positions and methyl groups at the 2,2'-positions were liquids at room temperature, and the neat liquids showed circularly polarized luminescence (CPL) (R=Bu; Φfl,liquid =0.21, |glum,liquid |=1.6×10-3 ). The |glum,liquid | value is the highest of pure liquids. These compounds remained liquid over a broad range of temperatures, down to -50 °C. Time-dependent DFT calculations indicated that in the excited state, the binaphthyls adopt a transoid conformation with a small angle between the electric and magnetic transition dipole moments (θµ,m =77°), which is a key factor in their CPL activity. The best binaphthyl dihedral angle in the excited state is approximately 110°.

Solvent-Induced Sign Inversion of Circularly Polarized Luminescence: Control of Excimer Chirality by Hydrogen Bonding.

A series of pyrenes sandwiched by axially chiral 1,1'-binaphthyls were synthesized. Among them, (R,R)-3 possessing 2-hydroxy-3,3'-dimethylbinaphthyls exhibited solvent-dependent inversion of the sign of circularly polarized luminescence (CPL) without a change in emission wavelength. The (-)- and (+)-CPL were detected in nonpolar and polar solvents, respectively, with glum values of -0.012 and +0.012. This switching property originates from the inversion of excimer chirality caused by the presence or absence of intermolecular hydrogen bonds in the excited state. The CPL intensity was also changed by variation of the temperature and concentration.

Tetrameric and Hexameric Porphyrin Nanorings: Template Synthesis and Photophysical Properties.

Hexameric and tetrameric porphyrin nanorings, Z6·T6 and Z4·T4, were synthesized in 53% and 14% yields, respectively, by the Sonogashira-type self-oligomerization of porphyrin monomer 1 using hexadentate template T6 and tetrapyridylporphyrin template T4. Template-free nanorings Z6 and Z4 were also prepared. The femtosecond transient absorption measurements revealed fast excitation energy hopping (EEH) along these nanorings with hopping rates of 2-5 ps. Treatment of Z6 with chiral template CT6 gave Z6·CT6 showing circular dichroism (CD) and circularly polarized luminescence (CPL) in the absorption and fluorescence regions of Z6, respectively, which indicates chirality transfer from CT6 to Z6.

Aggregation-Induced Circularly Polarized Luminescence from Boron Complexes with a Carbazolyl Schiff Base.

A variety of carbazolyl-appended Schiff bases were readily synthesized from 1-formylcarbazoles and aniline derivatives. Boron complexation of the resulting ligands allowed for facile preparation of new carbazole-based BODIPY analogues showing solid-state fluorescence. Furthermore, some dyes were converted into chiral compounds through the Et2 AlCl-mediated incorporation of a binaphthyl unit. The chiral dyes showed aggregation-induced fluorescence and circularly polarized luminescence (CPL) with the ΦF and glum of up to 0.22 and -3.5×10-3 , respectively, in the solid state. The solid-state fluorescence and CPL were well characterized by the crystal packing analyses and DFT calculations.

Synthesis and Chiroptical Properties of Chiral Carbazole-Based BODIPYs.

A series of carbazole-based boron dipyrromethenes (BODIPYs) 2 a-g bearing binaphthyl units have been synthesized by the Et2 AlCl-mediated reaction of the corresponding BODIPY difluorides 1 a-g with 1,1'-binaphthalene-2,2'-diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl-substituted 1 h gave (R,R)-3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher glum values in the solid state, probably due to intermolecular interactions. Because (R,R)-3 h recorded relatively low glum values, the diastereomer (R,S)-3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole-based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near-IR (NIR) region in the solid state.

Axially Chiral peri-Xanthenoxanthenes as a Circularly Polarized Luminophore.

A series of axially chiral peri-xanthenoxanthenes (PXXs) were synthesized from 1,1'-bi-2-naphthol without optical resolution. These are the first examples of chiral PXXs. Among them, PXX 5 with two naphthalene rings connected via a methylenedioxy bridge and a chiral axis displayed intense fluorescence (FL) and circularly polarized luminescence (CPL) both in solution (ΦFL of 0.72 and |glum| of 1.4 × 10-3) and in the solid state (ΦFL of 0.13 and |glum| of 4.8 × 10-3). The bridged structure of PXX 5 adjusts the angle between the vectors of the electric and magnetic transition dipole moments, which is essential for showing intense CPL activity.

Evolving Fluorophores into Circularly Polarized Luminophores with a Chiral Naphthalene Tetramer: Proposal of Excimer Chirality Rule for Circularly Polarized Luminescence.

A versatile method for converting various fluorescent polycyclic aromatic hydrocarbons into circularly polarized luminescence (CPL) excimer dyes with high glum and ΦFL values is reported. This method involves the functionalization of a chiral quaternaphthyl with six fluorophores via ester linkages in the last step of the synthesis. The usefulness of this approach was demonstrated for 1-, 2-, and 4-pyrenyl, 2- and 3-perylenyl, and 2-anthryl dyes. Most of them are the first or rare examples of CPL dyes. In the ground state, the fluorophores are tightly arranged by cumulative steric and electronic effects. In the excited state, the fluorophores form a twist excimer that maintains the ground-state conformations. The local chiral excimer directly affected the CPL properties. The systematic study on the signs of the CPLs allowed us to find a rule called the excimer chirality rule: right- and left-handed excimers exhibit (+)- and (-)-CPL, respectively.

Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations.

Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3 L3 or Ni3 L3 ) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.

Binaphthyl-Bipyridyl Cyclic Dyads as a Chiroptical Switch.

A series of chiral cyclic dyads, axially chiral binaphthyls linked to a 3,3'-bipyridyl, was synthesized. The dyad 2 bearing methoxy groups exhibited ON/OFF properties in circularly polarized luminescence (CPL), yielding a | glum| of 1.6 × 10-3 or 0 without any change in fluorescence. This type of CPL switch is unprecedented. Regioisomer 4 exhibited a dextro/ levo rotation switching ability in [α]D. X-ray structures as well as experimental and theoretical analyses suggested that the switching properties depended on conformational changes.

Cross-Coupling Approach to an Array of Macrocyclic Receptors Functioning as Chiral Solvating Agents.

Chiral macrocyclic receptors 1 with multiple hydrogen-bonding sites in the cavity were synthesized and used as NMR chiral solvating agents (CSAs). The Suzuki-Miyaura cross-coupling reaction gave rapid access to a series of variants 1b-p of unsubstituted parent compound 1a. Among them, 1d with the 4-cyanophenyl group at the 3,3'-positions of the binaphthyl moiety was the most excellent CSA for a benchmark analyte compound, 2-chloropropionic acid (CPA); both of the quartet and doublet signals of CPA were split most completely in CDCl3. Binding constants ( Ka) determined in CDCl3 by NMR titrations indicated that ( R)-1d was the most enantioselective ( Ka( S)/ Ka( R) = 5.4). Interestingly, the Ka value of ( R)-1d for ( S)-CPA (5900) was greater than that of ( R)-1a for ( S)-CPA (3080), which strongly suggests an attractive interaction between the 4-cyanophenyl group of ( R)-1d and ( S)-CPA. The X-ray crystal structure of 1d indicates that one of the two H atoms meta to the cyano group is directed toward the cavity. DFT calculations suggested that this H atom of the 4-cyanophenyl group of ( R)-1d forms a weak hydrogen bond with the Cl atom of ( S)-CPA (C-H···Cl-C hydrogen bond).

Helical Oligonaphthodioxepins Showing Intense Circularly Polarized Luminescence (CPL) in Solution and in the Solid State.

A series of oligonaphthodioxepins was synthesized, revealing a helically arranged octamer, (R,R,R,R,R,R,R)-3, which showed intense circularly polarized luminescence (CPL) both in solution and in the solid state. The fluorescence quantum yields (ΦFL ) in solution and in the solid state were 0.90 and 0.22, respectively, and the glum values in solution and in the solid state were +2.2×10-3 and +7.0×10-3 , respectively. This is one of the highest solid-state CPL glum values yet reported. The high ΦFL and glum values were due to the rigidity, as well as to the fact that (R,R,R,R,R,R,R)-3 was a non-planar molecule. Moreover, (R,R,R,R,R,R,R)-3 was highly stable both chemically and stereochemically.

Quasi-Phase Diagrams at Air/Oil Interfaces and Bulk Oil Phases for Crystallization of Small-Molecular Semiconductors by Adjusting Gibbs Adsorption.

The temperature and concentration dependencies of the crystallization of two small-molecular semiconductors were clarified by constructing quasi-phase diagrams at air/oil interfaces and in bulk oil phases. A quinoidal quaterthiophene derivative with four alkyl chains (QQT(CN)4) in 1,1,2,2-tetrachroloethane (TCE) and a thienoacene derivative with two alkyl chains (C8-BTBT) in o-dichlorobenzene were used. The apparent crystal nucleation temperature (Tn) and dissolution temperature (Td) of the molecules were determined based on optical microscopy examination in closed glass capillaries and open dishes during slow cooling and heating processes, respectively. Tn and Td were considered estimates of the critical temperatures for nuclear formation and crystal growth, respectively. The Tn values of QQT(CN)4 and C8-BTBT at the air/oil interfaces were higher than those in the bulk oil phases, whereas the Td values at the air/oil interfaces were almost the same as those in the bulk oil phases. These Gibbs adsorption phenomena were attributed to the solvophobic effect of the alkyl chain moieties. The temperature range between Tn and Td corresponds to suitable supercooling conditions for ideal crystal growth based on the suppression of nucleation. The Tn values at the water/oil and oil/glass interfaces did not shift compared with those of the bulk phases, indicating that adsorption did not occur at the hydrophilic interfaces. Promotion and inhibition of nuclear formation for crystal growth of the semiconductors were achieved at the air/oil and hydrophilic interfaces, respectively.

Oligonaphthofurans: fan-shaped and three-dimensional π-compounds.

Using a bottom-up method, we prepared a series of oligonaphthofurans composed of alternating naphthalene rings and furan rings. The largest compound (compound 25) contained 8 naphthalene units and 7 furan units. DFT calculations revealed that these compounds were fan-shaped molecules and each naphthalene ring was oriented in an alternate mountain-valley fold conformation because of steric repulsion by the hydrogens at the peri-positions. We investigated the optical properties that derived from their fan-shaped and mountain-valley sequences. As the number of aromatic rings of the oligonaphthofurans increased, the peaks of the longest wavelength absorptions in the UV-vis spectra (HOMO-LUMO energy gap) of these compounds steadily red-shifted, although the shapes of spectra were not sustained because of the decreasing molar absorption coefficients (ε's) of their λ(max). We compared our results with those reported for other types of oligoaromatic compounds such as acenes 1, ethene-bridged p-phenylenes 2, rylenes 3, oligofurans 4, and oligonaphthalenes 5. The slopes of the plots between the transition energies (HOMO-LUMO energy gap) of the oligoaromatic compounds and the reciprocal of the number of aromatic rings indicated that the efficiency of π conjugation of the oligonaphthofurans was comparable with that of linear and rigid acenes and rylenes. The higher-order compounds 22 and 25 aggregated even under high dilution conditions (~10(-6) M).

Ion-based materials derived from positively and negatively charged chloride complexes of π-conjugated molecules.

Oriented salts from planar charged species were prepared by combining positively and negatively charged receptor-anion complexes with similar geometries using dicationic and electronically neutral π-conjugated receptors. Phenylene- or pyrimidine-bridged bis(imidazolium) dicationic anion receptors formed monocationic receptor-Cl(-) complexes that were accompanied by a free Cl(-). This free Cl(-) was subsequently captured by pyrrole-based neutral anion receptors to form negatively charged receptor-Cl(-) complexes. The ion pair of the resulting positively and negatively charged planar receptor-Cl(-) complexes could produce a supramolecular octane gel, adopting a lamellar self-organized structure in its xerogel state. On the other hand, the solid-state ion pairs had hexagonal columnar mesophases, which formed via alternate stacking of the positively and negatively charged planar receptor-Cl(-) complexes. By use of the flash-photolysis time-resolved microwave conductivity technique, the one-dimensional charge-carrier transporting property, with a mobility of 0.05 cm(2) V(-1) s(-1), was determined for the newly prepared solid-state ion pairs.

Formation and geometrical control of polygon-like metal-coordination assemblies.

Polygon-like [2+2]- and [3+3]-type metal complexes were prepared from dipyrrin dimers connected by acute-angled spacers. The electrical conduction depends strongly on the packing alignment of the compounds, revealing the presence of effective hopping pathways for holes with relatively high mobility up to 0.11 cm(2) V(-1) s(-1) along the aligned axis of [3+3]-type metal-bridged assemblies. These observations correlated with the geometrical control of the π-conjugated metal complexes in the cyclic structures, which enables their ordered arrangement in the assemblies.