Remarkable Effects of External Magnetic Field on Circularly Polarized Luminescence of EuIII (hfa)3 with Phosphine Chirality.

Herein, magnetic circularly polarized luminescence (CPL) (MCPL) spectroscopy was conducted to analyze an EuIII (hfa)3 complex with three chiral PIII -ligands. Resultantly, (R)-chirality luminophores with S-up orientation and (S)-chirality luminophores with N-up orientation were observed to possess symmetrical mirror image spectra, i. e., they were enantiomers. Similarly, the (R)-chirality luminophores with N-up orientation and the (S)-chirality luminophores with S-up orientation were also enantiomers. Contrarily, (R)-S-up and (S)-S-up were diastereomers and did not possess a mirror-image relationship. Likewise, (R)-N-up and (S)-N-up were diastereomers. The J-dependency of gMCPL and gCPL datasets suggested that the N-up/S-up external magnetic field, with the aid of chiral PIII -ligands, increased the gMCPL values by two- to sixteen-fold and modulated the gMCPL signs at J=1-4. Additionally, the origins of the nonideal mirror-symmetric CPL and MCPL spectral characteristics of EuIII (hfa)3 with three chiral PIII -ligands were discussed in terms of parity (space-inversion, P)-symmetry, time-reversal (T)-symmetry, and PT-symmetry laws.

Magnetic Circularly Polarized Luminescence in the Photoexcited States of Racemic [n]Helicenes (n=3-5,7) in Tetrahydrofuran and Dimethyl Sulfoxide Solutions.

This paper reports the first magnetic circularly polarized luminescence (MCPL) characteristics of racemic helicenes, including four unsubstituted [n]helicenes (n=3,4,5,7) and two [4]helicene derivatives bearing methoxy substituents, in tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) solutions. The value of |gMCPL | was calculated to be of the order of 10-3  T-1 within 350-430 nm under the north-up (N-up) and south-up (S-up) Faraday geometries in an external magnetic field of 1.6 T. The [n]-dependent MCPL signs were altered by the N-up and S-up geometries.

Stereospecific Synthesis of Cyclic Sulfite Esters with Sulfur-Centered Chirality via Diastereoselective Strategy and Intramolecular H-Bonding Assistance.

Stereospecific synthesis of several cyclic sulfite esters containing three stereogenic centers from enantiopure 1,1,4,4-tetraarylbutanetetraols was achieved. Chiral sulfur centers were constructed stereospecifically via a diastereoselective reaction with the assistance of an intramolecular H-bonding interaction. The absolute configuration of the S atom was elucidated by using the corresponding single-crystal X-ray diffraction analysis of the synthesized monochloride cyclic sulfite esters. Furthermore, a crystallographic evidence of the specific intramolecular C(sp3)-H···CAr weak H-bondings was presented, and its dramatic effect on the 1H NMR spectral properties was revealed. This intriguing behavior was unambiguously rationalized by different shielding effects of the neighboring phenyl rings. Additionally, the theoretical results obtained on the basis of MP2 calculations fully supported the existence of intramolecular hydrogen bonding interactions being responsible for the observed unique chemical and spectral properties.

Sign inversion of magnetic circularly polarized luminescence in Iridium(iii) complexes bearing achiral ligands.

Optically inactive, paramagnetic Ir(iii)(ppy)3 and Ir(iii)(ppy)2(acac) (ppy: 2-phenylpyridinate and acac: acetylacetonate) showed nearly mirror-symmetric magnetic circularly polarised luminescence (MCPL) spectra in dilute dichloromethane and dimethyl sulfoxide under N-up and S-up geometries in a 1.6-T magnetic field. However, the MCPL signs of Ir(iii)(ppy)3 and Ir(iii)(ppy)2(acac) under the same N-up (or S-up) Faraday geometry were opposite to each other when one ppy was replaced with an acac. This ligand exchange approach provides facile control of the MCPL sign, irrespective of the Faraday geometry.

Sign dependence of MCPL spectra on type and position of substituent groups of pyrene and phenanthrene derivatives.

Diamagnetic achiral pyrene and phenanthrene derivatives substituted with electron-donating hydroxyl/methoxy groups and electron-withdrawing carboxylic acid groups exhibited clear magnetic circularly polarised luminescence (MCPL) spectra at 360-460 nm in dilute solvents upon the application of N-up and S-up Faraday geometries under an external magnetic field of 1.6 T. Their MCPL signs were also susceptible upon application of the same Faraday geometry.

Circularly polarised luminescence from planar-chiral Phanephos/Tb(iii)(hfa)3 hybrid luminophores.

Planar-chiral Phanephos, containing the coordinatable P(iii), formed P(iii)/Tb(iii)(hfa)3 hybrid luminophores that successfully emitted characteristic circularly polarised luminescence (CPL) due to 5D4→7F5 transitions in solution. On the other hand, BINAP, containing P(iii)[double bond, length as m-dash]O as axially chiral ligand, exhibited no detectable CPL with Tb(iii)(hfa)3.

Ambidextrous Chirality Transfer Capability from Cellulose Tris(phenylcarbamate) to Nonhelical Chainlike Luminophores: Achiral Solvent-Driven Helix-Helix Transition of Oligo- and Polyfluorenes Revealed by Sign Inversion of Circularly Polarized Luminescence and Circular Dichroism Spectra.

We investigated whether helicity and/or chirality of cellulose tris(phenylcarbamate) (CTPC) can transfer to noncharged, nonhelical oligo- and polyfluorenes when CTPC was employed as a solution processable homochiral platform of a D-glucose-skeletal polymer. Noticeably, CTPC revealed the solvent-driven, ambidextrous intermolecular helicity/chirality transfer capability to these fluorenes. The chiroptical inversion characteristics of circularly polarized luminescence (CPL) and the corresponding CD spectra were realized by solely choosing a proper achiral solvent and/or achiral cosolvent. When the solution of PF6 and CTPC in tetrahydrofuran (THF) was cast on a quartz substrate, the dissymmetry ratio of CPL (gCPL) from the polymer film showed gCPL = +2.1 × 10-3 at 429 nm. Conversely, when dichloromethane (DCM) was used as the solvent, the CPL sign was inverted to gCPL = -2.4 × 10-3 at 429 nm. The dissymmetry ratio of Cotton CD band (gCD) from the THF solution was gCD = +3.2 × 10-3 at 392 nm; conversely, from the DCM, the CD sign inverted to gCD = -0.8 × 10-3 at 371 nm. The sign and magnitude of the gCD values were interpreted to a London dispersion term (δd) of Hansen solubility parameter (δ) of the casting solvents rather than a dipole-dipole interaction term (δp) and a hydrogen bonding interaction term (δh) of the δ values and dielectric constant (ε). Analysis of solvent-driven changes in FTIR spectra, wide-angle X-ray diffraction profiles, and differential scanning calorimetry diagrams indicated that solvent driven on-off switching of multiple hydrogen bonds due to three urethane groups of CTPC play the key for the inversion. Intermolecular CH/π and π-π interactions among phenyl rings and alkyl groups were assumed to be crucial for helicity/chirality transfer capability based on molecular mechanics and molecular dynamics simulations of PF6-CTPC hybrids. These chiroptical inversion characteristics arose from solvent-driven order-disorder transition characteristics of the CTPC helix rather than a helix-helix transition of CTPC itself.

Solvent-sensitive signs and magnitudes of circularly polarised luminescence and circular dichroism spectra: probing two phenanthrenes as emitters endowed with BINOL derivatives.

A C2-symmeric binaphthyl framework bearing phenanthrene as the emitter exhibited circularly polarised luminescence (CPL) in dilute solutions. The CPL and circular dichroism signs of the luminophores were altered by solvents (chloroform, methanol, acetonitrile, and dimethylformamide). DFT and TD-DFT calculations indicated that the dihedral angle between the phenanthrene and naphthyl rings was responsible for the apparent sign inversion. The role of solvent molecules in the ground and photoexcited states was discussed based on Hansen solubility parameters (δ, δd, δp and δh).

Combined Experimental and Theoretical Study on Circular Dichroism and Circularly Polarized Luminescence of Configurationally Robust D3-Symmetric Triple Pentahelicene.

Pentahelicene (PH) exhibits the largest absorption ( gabs) and luminescence ( glum) dissymmetry factors among the helicene family but is configurationally and (photo)chemically labile, encumbering its application to chiroptical materials. To bypass the pitfalls, three PH units are merged in a single molecule to build D3-symmetric triple pentahelicene, hexabenzotriphenylene (HBT), which attains indeed the configurational and (photo)chemical robustness through equilibrium with a C2-symmetric conformer that interrupts the racemization and photocyclization. UV-vis, circular dichroism (CD), and circularly polarized luminescence (CPL) spectral examinations reveal the significantly larger gabs and glum values for HBT than for any of configurationally robust single [ n]helicene ( n ≥ 6) and C2-symmetric triple pentahelicene, trinaphthotriphenylene (TNT). Theoretical calculations precisely reproduce the main features of the experimental CD and CPL spectra of PH, HBT, and TNT, and the relevant electric and magnetic transition moments and their mutual angles well rationalize the relative CD and CPL intensities of all the single and triple pentahelicenes.

Questions of Mirror Symmetry at the Photoexcited and Ground States of Non-Rigid Luminophores Raised by Circularly Polarized Luminescence and Circular Dichroism Spectroscopy: Part 1. Oligofluorenes, Oligophenylenes, Binaphthyls and Fused Aromatics.

We report experimental tests of whether non-rigid, π-conjugated luminophores in the photoexcited (S1) and ground (S0) states dissolved in achiral liquids are mirror symmetrical by means of circularly polarized luminescence (CPL) and circular dichroism (CD) spectroscopy. Herein, we chose ten oligofluorenes, eleven linear/cyclic oligo-p-arylenes, three binaphthyls and five fused aromatics, substituted with alkyl, alkoxy, phenyl and phenylethynyl groups and also with no substituents. Without exception, all these non-rigid luminophores showed negative-sign CPL signals in the UV-visible region, suggesting temporal generation of energetically non-equivalent non-mirror image structures as far-from equilibrium open-flow systems at the S1 state. For comparison, unsubstituted naphthalene, anthracene, tetracene and pyrene, which are achiral, rigid, planar luminophores, did not obviously show CPL/CD signals. However, camphor, which is a rigid chiral luminophore, showed mirror-image CPL/CD signals. The dissymmetry ratio of CPL (glum) for the oligofluorenes increased discontinuously, ranging from ≈ -(0.2 to 2.0) × 10-3, when the viscosity of the liquids increased. When the fluorene ring number increased, the glum value extrapolated at [η] = 0 reached -0.8 × 10-3 at 420 nm, leading to (⁻)-CPL signals predicted in the vacuum state. Our comprehensive CPL and CD study should provide a possible answer to the molecular parity violation hypothesis arising due to the weak neutral current mediated by the Z°-boson.

Correction: Fujiki, M., et al. Questions of Mirror Symmetry at the Photoexcited and Ground States of Non-Rigid Luminophores Raised by Circularly Polarized Luminescence and Circular Dichroism Spectroscopy: Part 1. Oligofluorenes, Oligophenylenes, Binaphthyls and Fused Aromatics. Molecules, 2018, 23, 2606.

The authors wish to make the following correction to their paper [...].

Circularly Polarized Light with Sense and Wavelengths To Regulate Azobenzene Supramolecular Chirality in Optofluidic Medium.

Circularly polarized light (CPL) as a massless physical force causes absolute asymmetric photosynthesis, photodestruction, and photoresolution. CPL handedness has long been believed to be the determining factor in the resulting product's chirality. However, product chirality as a function of the CPL handedness, irradiation wavelength, and irradiation time has not yet been studied systematically. Herein, we investigate this topic using achiral polymethacrylate carrying achiral azobenzene as micrometer-size aggregates in an optofluidic medium with a tuned refractive index. Azobenzene chirality with a high degree of dissymmetry ratio (±1.3 × 10-2 at 313 nm) was generated, inverted, and switched in multiple cycles by irradiation with monochromatic incoherent CPL (313, 365, 405, and 436 nm) for 20 s using a weak incoherent light source (≈ 30 µW·cm-2). Moreover, the optical activity was retained for over 1 week in the dark. Photoinduced chirality was swapped by the irradiating wavelength, regardless of whether the CPL sense was the same. This scenario is similar to the so-called Cotton effect, which was first described in 1895. The tandem choice of both CPL sense and its wavelength was crucial for azobenzene chirality. Our experimental proof and theoretical simulation should provide new insight into the chirality of CPL-controlled molecules, supramolecules, and polymers.

Circularly polarised luminescence of pyrenyl di- and tri-peptides with mixed d- and l-amino acid residues.

Multiple pyrenes as pendants of enantioimpure di-/tripeptides (abbreviated as N-LD-C, N-DL-C, N-LLD-C and N-DDL-C) showed pyrene-origin CPL and CD signals, which were associated with conflicting CPL-/CD-signs, compared to the corresponding enantiopure di-/tri-peptides.

Synthesis of Well-Defined Oligo(2,5-dialkoxy-1,4-phenylene vinylene)s with Chiral End Groups: Unique Helical Aggregations Induced by the Chiral Chain Ends.

Oligo(2,5-dialkoxy-1,4-phenylenevinylene)s containing three different chiral alkoxy substituents on the phenyl end groups with structurally regular (all trans) controlled repeat units have been prepared; these compounds showed highly enhanced aggregation-induced circular dichroism (AICD; formation of supramolecular polymers), and an inversion of the CD signal was observed even with the same end groups under certain conditions.

Circularly polarised luminescence and circular dichroism of l- and d-oligopeptides with multiple pyrenes.

Among l- and d-oligopeptides with multiple pyrenes as pendants, the dipeptides with two and three pyrenes showed blue-coloured circularly polarised luminescence as high as |gem|≈ (0.86-1.1) × 10(-2) at around 450 nm, reflecting from exciton couplets of twisted pyrenes.

Solid-state circularly polarised luminescence of atropisomeric fluorophores embedded in achiral myo-inositol-containing polyurethanes.

We investigated the ground- and photoexcited-state chiralities of two chiral fluorophores with a rigid framework embedded in two achiral polyurethanes as the solid matrices. As the fluorophores, we used two pairs of atropisomeric binaphthyl derivatives, (R)-(−)-1,1'-binaphthyl-2,2'-diyl hydrogen phosphate [(R)-1a] and (R)-(−)-(3,5-dioxa-4-phosphacyclohepta-[2,1-a:3,4-a']dinaphthalen-4-yl)-dimethylamine [(R)-1b], and for comparison, their optical antipodes (S)-1a and (S)-1b. As the solid matrices, we used two soluble achiral polyurethanes (2a and 2b) derived from the naturally occurring myo-inositol as the building block, because these polymers had a high glass transition temperature of ~150 °C. The chiral fluorophores in the polyurethanes emitted circularly polarised luminescence with a high circular anisotropy of ~0.6­1.5 × 10(-3). Regardless of the matrix, (R)- and (S)-1a had nearly mirror-image chiroptical properties in the ground and photoexcited states, as did (R)- and (S)-1b.

Enhancing circularly polarised luminescence by extending the π-conjugation of axially chiral compounds.

Circularly polarised luminescence (CPL) and photoluminescence (PL) properties of π-conjugated (R)- and (S)-2,2'-diphenyl-4-biphenanthrol (VAPOL) exhibited an efficient CPL (∼1.3 × 10(-3)) with a quantum yield (ΦF) of 0.20 at 376 nm. By comparison, (R)- and (S)-3,3-diphenyl-2,2-bi-1-naphthol (VANOL) exhibited no CPL or PL.

Time-resolved observation of chiral-index-selective wrapping on single-walled carbon nanotube with non-aromatic polysilane.

In the present paper, we ascertain two novel findings on chiral-index-selective binding/separating of single-walled carbon nanotubes (SWNTs) with a nonaromatic polymer, poly(dialkylsilane) (PSi). PSi is a typical σ-conjugated polymer, composed of alkyl side chains attached to the silicon (Si)-catenated main chain. First, PSi's with linear alkyl side chains showed significant diameter-selective wrapping for SWNTs with ca. 0.9 nm in diameter, resulting in the selective separation of (7,6) and (9,4) SWNTs. Its driving force was demonstrated to be cooperative CH-π interactions among the alkyl side chains of PSi's and the curved graphene of SWNTs. Second, the dynamic wrapping behavior of PSi's onto SWNTs was elucidated with time-resolved UV spectroscopy. Highly anisotropic UV absorption of PSi along the Si main chain was utilized as a "chromophoric indicator" to monitor the global/local conformations, which enabled us to track kinetic structural changes of PSi's on SWNTs. Consequently, we concluded that upon wrapping, flexible/helical PSi with an average dihedral angle (φ) of 145° and Kuhn's segment length (λ(-1)) of 2.6 nm interconverted to the more stiffer/planar conformation with 170° and λ(-1) of 7.4 nm. Furthermore, through kinetic analyses of the time-course UV spectra, we discovered the fact that PSi's involve three distinct structural changes during wrapping. That is, (i) the very fast adsorption of several segments within dead time of mixing (<30 ms), following (ii) the gradual adsorption of loosely wrapped segments with the half-maximum values (τ(1)) of 31.4 ms, and (iii) the slow rearrangement of the entire chains with τ(2) of 123.1 ms, coupling with elongation of the segment lengths. The present results may be useful for rational design of polymers toward chiral-index-selective binding/separating of desired (n,m) SWNTs.

Chiroptical inversion in helical Si-Si bond polymer aggregates.

To elucidate the factors involved in the chiroptical properties of polymer aggregates composed of helical building blocks, a series of rigid rod helical poly[alkyl-(S)-2-methylbutylsilane]s (achiral alkyl side chains = ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl) have been investigated. It was found that the chiroptical sign in the circular dichroism (CD) spectra of the polysilane aggregates depends on the achiral side chain length and cosolvent fraction. Concerning the achiral side chains, the n-propyl group was of a critical length for solvent-dependent chiroptical inversion on aggregation. This unique side chain length-dependent chiroptical inversion was theoretically predictable by using the novel approach of combining the cholesteric hard-core model and exciton chirality method. The latter was also investigated theoretically by Gaussian 03 (TD-DFT, B3LYP, 6-31G(d) basis set) calculations applied to two spatially arranged helical Si-Si bonded decamer models.

Chiral self-assembly of designed amphiphiles: influences on aggregate morphology.

A series of novel amphiphiles were designed for self-assembly into chiral morphologies, the amphiphiles consisting of a glutamic acid (Glu) headgroup connected through an 11-carbon alkoxy chain to a diphenyldiazenyl (Azo) group and terminated with a variable length alkyl chain (R-Azo-11-Glu, where R denotes the number of carbons in the distal chain). TEM imaging of amphiphile aggregates self-assembled from heated, methanolic, aqueous solution showed that chiral order, expressed as twisted ribbons, helical ribbons, and helically based nanotubes, increased progressively up to a distal chain length containing eight carbons, and then decreased with further increases in distal chain length. TEM and CD showed that the chiral aggregations of single enantiomers were influenced by the molecular chirality of the headgroup. However, the assembly of D,L-10-Azo-11-Glu into nanotubes demonstrated that chiral symmetry breaking effected by the azo group was also relevant to the chiral organization of the amphiphiles. The chiral order of aggregate morphologies was additionally affected by the temperature and solvent composition of assembly in a manner correlated to the mechanism driving assembly; i.e., D,L-10-Azo-11-Glu was sensitive to the temperature of assembly but less so to solvent composition, while L-14-Azo-11-Glu was sensitive to solvent composition and not to temperature. FTIR and UV-vis spectroscopic investigations into the organization of the head and azo groups, in chiral and achiral structures, illustrated that a balance of the influences of the hydrophilic and hydrophobic components on self-assembly was required for the optimization of the chiral organization of the self-assembled structures.