Semiconducting Carbon Nanotube Extraction Enabled by Alkylated Cellulose Wrapping.

With the growing demand for postsilicon electronics, the purification of single-walled carbon nanotubes (SWCNTs) in terms of their chirality, which defines their atomic and electronic structure, is becoming increasingly important. Herein, we demonstrate the selective extraction of high-quality semiconducting SWCNTs using alkyl cellulose as a dispersant in organic solvents. We investigated the separation factors of dispersant structures, such as the degree of substitution (DS) and molecular weight, and clarified the appropriate dispersant structures, such as moderately substituted hexyl cellulose, for selective semiconducting SWCNT extraction. Due to the improved purity and quality of the semiconducting SWCNTs obtained by this method, their films exhibit excellent thermoelectric power factors, outperforming not only unsorted SWCNTs but also conducting polymer-sorted SWCNTs. This sorting technology paves the way for supplying high-quality semiconducting SWCNTs in a viable manner.

C3-Symmetric Luminescent Diketone with Amido-Linkage as a Polymorphic Fluorescence Emitter.

The study introduces a novel C3-symmetric ß-diketone compound, BTA-D3, and its monomeric counterpart, D, with a focus on their synthetic procedure, photophysical properties and aggregation behavior. Both compounds exhibit characteristic absorption and weak fluorescence in solution, with BTA-D3 displaying higher absorption coefficients due to its larger number of diketone units. Density Functional Theory (DFT) calculations suggest increased co-planarity of diketone groups in BTA-D3. A significant finding is the Aggregation-Induced Emission (AIE) property of BTA-D3, as its fluorescence intensity increases dramatically when exposed to specific solvent ratios. The AIE behavior is attributed to intermolecular excitonic interaction between BTA-D3 molecules in self-organized aggregates. We also studied fluorescence anisotropy of BTA-D3 and D. Despite its larger size, BTA-D3 showed reduced anisotropy values because of efficient intramolecular energy migration among three diketone units. Furthermore, BTA-D3 demonstrates unique polymorphism, yielding different emission colors and structures depending on the solvent used. A unique approach is presented for promoting the growth of self-organized aggregate structures via solvent evaporation, leading to distinct fluorescence properties. This research contributes to the understanding of C3-symmetric structural molecules and provides insights into strategies for controlling molecular alignment to achieve diverse fluorescence coloration in molecular materials.

Synthesis and Spectroscopic Properties of Diarylethene-Subporphyrinoid Hybrids.

Two novel diarylethene-fused subporphyrinoids were prepared and characterized. A mono diarylethene derivative was obtained via a statistical condensation reaction with 2 eq. of 1,2-dicyanobenzene and 1 eq. of thiophene-disubstituted butenedinitrile. The symmetric triply diarylethene-fused subporphyrazine was synthesized via a cyclotrimerization reaction of the thiophene-disubstituted butenedinitrile derivative. These compounds were characterized by NMR spectroscopy and high-resolution mass spectrometry. The spectroscopic properties have been measured in hexane and in chloroform. The mono diarylethene-fused-type compound showed photochromism at 580 nm and >700 nm wavelength, accompanied by degradation. According to DFT calculations, photoreactivity likely depends on the contribution of aromatic feature of pyrrole ring bonded to two thiophene rings.

Synthetic Utilization of 2H-Heptafluoropropane: Ionic 1,4-Addition to Electron-Deficient Carbon-Carbon Unsaturated Bonds.

We have found a novel method for introducing heptafluoro-2-propyl CF(CF3)2 groups into carbon-carbon unsaturated bonds via a nucleophilic reaction using 2H-heptafluoropropane as the source of CF(CF3)2 groups. The reaction involves the nucleophilic addition of a heptafluoro-2-propyl anion, generated by treating 2H-heptafluoropropane with a fluoride ion, to various electron-deficient unsaturated compounds. This allows the easy synthesis of various aliphatic compounds containing heptafluoro-2-propyl groups.

Excited State Engineering in Ag29 Nanocluster through Peripheral Modification with Silver(I) Complexes for Bright Near-Infrared Photoluminescence.

The optical property of an ionic metal nanocluster (NC) is affected by the ionic interaction with counter ions. Here, we report that the modification of trianionic [Ag29(BDT)12(TPP)4]3- NC (BDT: 1.3-benzenedithiol; TPP: triphenylphosphine) with silver(I) complexes led to the intense photoluminescence (PL) in the near-infrared (NIR) region. The binding of silver(I) complexes to the peripheral region of Ag29 NC is confirmed by the single-crystal X-ray diffraction (SCXRD) measurement, which is further supported by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) spectroscopy. The change of excited-state dynamics by the binding of silver(I) complexes is discussed based on the results of a transient absorption study as well as temperature-dependent PL spectra and PL lifetime measurements. The modification of Ag29 NCs with cationic silver(I) complexes is considered to give rise to a triplet excited state responsible for the intense NIR PL. These findings also afford important insights into the origin of the PL mechanism as well as the possible light-driven motion in Ag29-based NCs.

Synthesis and Photochromic Properties of Diaryl [5]Helicene Derivatives.

Photoinduced tuning of aromaticity and correlative molecular properties has attracted enormous interest in recent years both for modulating photochromism properties and designing novel photochromic materials. Here, we report the synthesis and photochemical characterization of diaryl[5]helicene-based diarylethene molecular switches. 3,4-Bis(2,4-dimethyl-5-phenylthiophen-3-yl)dibenzo[c,g]phenanthrene derivative 1 a showed no photochromic reaction, whereas 3,4-bis(2-methyl-5-phenylthiophen-3-yl)dibenzo[c,g]phenanthrene derivative 2 a and 3,4-bis(5-methyl-2-phenylthiazol-4-yl)dibenzo[c,g]phenanthrene derivative 3 a exhibited reversible photochromism in different aprotic solvents with specific light irradiation. Meanwhile, the diarylethene compounds 2 a and 3 a underwent turn-off mode fluorescence photoswitching together with photoisomerization upon light irradiation. Remarkably, the photoinduced changes in the aromaticity of [5]helicene as a central ethene bridge along with the relative smaller activation energy and higher frequency factor facilitated the thermal bleaching rates of diarylethene switches 2 and 3 in solution. This research provides new insight for designing aromatic diarylethene photoswitches for reversible fluorescence switching, photoinduced changes in aromaticity and further fast thermal back reactions.

From Visible to Near-Infrared Light-Triggered Photochromism: Negative Photochromism.

Photochromic compounds, whose key molecular properties can be effectively modulated by light irradiation, have attracted significant attention for their potential applications in various research fields. The restriction of photoisomerization coloration induced by ultraviolet light limits their applications in the biomedical field and some other fields. Negative photochromism, wherein a relatively stable colored isomer transforms to a colorless metastable isomer under low-energy light irradiation, offers advantages in applications within materials science and life science. This review provides a summary of negatively photochromic compounds based on different molecular skeletons. Their corresponding design strategies and photochromic properties are presented to provide practical guidelines for future investigations. Negatively photochromic compounds can effectively expand the range of photochromic switches for future applications, offering unique properties such as responsiveness to visible to near-infrared light.

Tetrathienyl Corannulene Compounds with Highly Sensitive Photochromism.

We have designed and synthesized photochromic tetrathienyl corannulene compounds, 1,2,7,8-tetrakis(2-methyl-5-phenylthiophen-3-yl)corannulene (1) and 1,2,7,8-tetrakis(2,4-dimethyl-5-phenylthiophen-3-yl)corannulene (2), by fusing two units of photochromic terarylene with a curved aromatic corannulene with a promising antenna effect. Compound 1 exhibited highly sensitive photoreactivity, with a large molar absorption coefficient of 8.2×104  M-1 cm-1 and practically photon-quantitative photocyclization. On the other hand, a terarylene derivative with a planar aromatic phenanthrene, 9,10-bis(2,4-dimethyl-5-phenylthiophen-3-yl)phenanthrene (4) showed no photoreactivity. The reason for such a difference was attributed to the predominance of the photoreactive atropisomers amplified by energy migration, and the shortened distance between reactive carbons induced by the curved structure.

Chiral Dinuclear EuIII , TbIII , and YIII Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide.

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)4 , was synthesized to prepare C2 dinuclear M(hfa)3 complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)3 complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)2 , were also prepared, and comparison of their photophysical properties for the EuIII complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)3 units through intramolecular π-π stacking constraint in the dinuclear system.

Circularly Polarized Luminescence and Circular Dichroism of Bichromophoric Difluoroboron-ß-diketonates: Inversion and Enhanced Chirality Based on Spatial Arrangements and Self-Assembly.

We synthesized two bichromophoric difluoroboron-ß-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge (para and meta (R/S)-CyDFB). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher gabs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the glum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the glum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores.

Self-Regulated Pathway-Dependent Chirality Control of Silver Nanoclusters.

Imparting chirality affords additive values, functions and responsiveness in molecular systems including nanoscale materials. Here, we report pathway-dependent chirality control in silver nanoclusters (NCs). The use of enantiomeric ligand, α-dihydrolipoic acid (DHLA), for the synthesis of Ag NCs leads to the preferential formation of one-handed chiral Ag29 (DHLA)12 NCs with intrinsic chirality in the exterior shell composed of a silver-dithiolate framework. Small Lewis base molecules such as pyridine bind to silver atoms in the shell of NC as a guest. The guest binding reverses the relative stability between the right- and left-handed NCs upon a steric interaction with the chiral ligand DHLA in the exterior shell in a kinetic manner, leading to unprecedented chirality inversion in the synthesis of NCs. This mechanism is further extended to the self-regulation or self-replication of chirality through interNC interactions dependent on the concentration in the synthesis of NCs.

Molecular Rotor Functionalized with a Photoresponsive Brake.

A molecular motor that has been previously shown to rotate when fueled by electrons through a scanning tunneling microscope tip has been functionalized with a terarylene photochrome fragment on its rotating subunit. Photoisomerization has been performed under UV irradiation. Variable-temperature 1H NMR and UV-vis studies demonstrate the rotational motion and its braking action after photoisomerization. The braking action can be reversed by thermal heating. Once the rigid and planar closed form is obtained, the rotation is effectively slowed at lower temperature, making this new rotor a potential motor with an independent response to electrons and light.

Visible Circularly Polarized Luminescence of Octanuclear Circular Eu(III) Helicate.

This work reports on the structural and photophysical characterization of D4-symmetrical octanuclear circular LnIII helicates, [(R)- or (S)-iPr-Pybox]8(LnIII)8(THP)8 (where Ln = Eu and Tb, THP = trianionic tris-ß-diketonate, and iPr-Pybox = chiral bis(4-isopropyl-2-oxazolinyl)pyridine). X-ray crystallographic analysis revealed that the octanuclear circular helicate possesses square antiprism architecture and consists of four [(R)- or (S)-iPr-Pybox]2LnIII2(THP)2 asymmetric units arranged in a closed ring form. Ligand-to-ligand interactions between the THP and the iPr-Pybox ligands have successfully directed formation of enantiopure, homoconfigurational (Δ,Δ,Δ,Δ,Δ,Δ,Δ,Δ)-R and (Λ,Λ,Λ,Λ,Λ,Λ,Λ,Λ)-S isomers. All of the nonacoordinated LnIII ions are identical and exhibit a distorted capped square antiprism (CSAP) geometry. Upon excitation of the ligand absorption band (λ = 360 nm), the circular helicates display characteristic EuIII (red, 5D0 → 7FJ, J = 0-4) or TbIII (green, 5D4 → 7FJ, J = 6-3) core f-f luminescence. The overall emission quantum yields of the circular EuIII and TbIII helicates are 0.145 and 0.0013, respectively, in chloroform. The EuIII and TbIII complexes exhibit remarkable circularly polarized luminescence (CPL) activity at their magnetic dipole transition with observed luminescence dissymmetry factors |glum| of 1.25 (5D0 → 7F1, λ = 592 nm) and 0.25 (5D4 → 7F5, λ = 541 nm), respectively. Exceptional |glum| values of the circular EuIII helicates highlight the visible intensity difference between left and right circularly polarized emissions of R and S isomers in chloroform and PMMA thin film.

Self-assembled Tetranuclear EuIII Complexes with D2- and C2h-Symmetrical Square Scaffold.

Three new tetranuclear europium(III) alternating circular helicates, (2-PhRRRR/2-PhSSSS) [(R)- or (S)-Ph-Pybox]4EuIII4(BPP)6, (2-iPrRRRR/2-iPrSSSS) [(R)- or (S)-iPr-Pybox]4EuIII4(BPP)6, and (3-PhRRRR/3-PhSSSS) [(R)- or (S)-Ph-Pybox]4EuIII4(BHP)6, are presented with their structural and chiroptical characterization (BPP and BHP = bis-ß-diketonates; Pybox = chiral bis(oxazolinyl) pyridine ligand). X-ray crystallographic analysis revealed that different extents of interligand-contacting interactions between bis-ß-diketonates and Pybox ligands produce different bis-ß-diketonates arrangements around four EuIII ions and, thus, their specific symmetry in the final tetranuclear complexes. 2-PhRRRR/2-PhSSSS and 3-PhRRRR/3-PhSSSS are recognized as D2-symmetry, while 2-iPrRRRR/2-iPrSSSS self-assemblies possess pseudo C2h-symmetry. Due to different molecular symmetry, 2-PhRRRR/2-PhSSSS and 2-iPrRRRR/2-iPrSSSS crystals display different ligands orientation in their EuIII coordination spheres. The presence of pseudo σh-mirror symmetry in 2-iPrRRRR/2-iPrSSSS promotes a pair of distinguishable EuIII geometries. All the chiral self-assemblies exhibit almost identical photoluminescence emission spectra patterns of f-f transitions in the EuIII core. The EuIII self-assemblies exhibit intense CPL with different observed |glum| values (2-PhRRRR/2-PhSSSS ∼ |0.31|, 2-iPrRRRR/2-iPrSSSS ∼ |0.08|, 3-PhRRRR/3-PhSSSS ∼ |0.31| in chloroform).

Solvation of quantum dots in 1-alkyl-1-methylpyrrolidinium ionic liquids: toward stably luminescent composites.

CdTe nanoparticles capped with a cationic thiolate ligand were stably dispersed in ionic liquids, 1-alkyl-1-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)amides with an alkyl group of n-propyl, butyl and octyl-chain, and in an ionic plastic crystal, 1-ethyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide. Dispersion behavior of CdTe nanoparticles in these ionic media was evaluated, in which the solvation of nanoparticles by the ionic components was particularly interested. The ionic media showed alkyl-chain length-dependent solvation behavior, which was suggested by the thermal analysis of nanocomposites. The longer alkyl-chains led to the greater decrease in the thermal melting enthalpy of ionic media with the introduction of nanoparticles. The ionic liquid with an octyl-chain, which is considered to form a thicker solvation layer, afforded better emission durability of CdTe nanoparticles compared to the ionic liquid with a shorter alkyl chain.

Photo-Lewis Acid Generator Based on Radical-Free 6π Photo-Cyclization Reaction.

We present here a new photo-active molecule which acts as a photo-Lewis acid generator (PLAG) based on photo-chemical 6π-percyclization. Photo-illumination of the PLAG molecule produces a condensed aromatic carbocation with a triflate counteranion, which exhibits Lewis acid chemical catalytic reactivity such as initiation of the polymerization of epoxy monomers and catalysis of Mukaiyama-aldol reactions. The terminal-end structure in the epoxy polymerization was modified with the Lewis acid fragment. The carbocation induced the Mukaiyama-aldol reaction as a new photo-gated system with remarkably high catalytic reactivity and turnover numbers higher than 60. The photo-chemical quantum yield of the carbocation generation is 50%, which is considerably higher than obtained with most Brønsted photo-acid generators.

Finely Controlled Circularly Polarized Luminescence of a Mechano-Responsive Supramolecular Polymer.

Finely controlled circularly polarized luminescence (CPL) supramolecular polymerization based on a tetraphenylethene core with four l- or d-alanine branch side chains (l-1 and d-1) in the solution state is presented, resulting from the tuning of mechanical stimulus. Weak, green emissions of l-1 and d-1 in tetrahydrofuran (THF) were converted into strong blue emissions by tuning the mechanical stimulus. The strong blue emissions were caused by an aggregation-induced emission (AIE) effect during the formation of a supramolecular polymer. Lag time in the supramolecular polymerization was drastically reduced by the mechanical stimulus, which was indicative of the acceleration of the supramolecular polymerization. A significant enhancement of circular dichroism (CD) and CPL signals of l-1 and d-1 was observed by tuning the rotational speed of the mechanical stimulus, implying that the chiral supramolecular polymerization was accelerated by the mechanical stimulus.

Ligand-to-Ligand Interactions That Direct Formation of D2-Symmetrical Alternating Circular Helicate.

This work demonstrates that ligand-to-ligand interactions between achiral bis-ß-diketonate (BTP) and chiral bis(4-phenyl-2-oxazolinyl)pyridine [( R)- or ( S)-Ph-Pybox] are successfully directed to the fabrication of a D2-symmetrical alternating circular helicate with the general formula [( R)- or ( S)-Ph-Pybox]4(LnIII)4(BTP)6. The lanthanide(III) LnIII assemblies (LnIII4- RRRR and LnIII4- SSSS) have a nanometer-size squarelike grid (interatomic distances > 10 Å). X-ray structure analysis revealed that the circular helicate contains two double helicate LnIII2L2 units, where both show ( M)-helicity for LnIII4- RRRR and ( P)-helicity for LnIII4- SSSS, where π-π stacking interaction is present between the side arm of ( R)-Ph-Pybox (Ph1) and the adjacent BTP ligand around the EuIII metal center ( dππ = 3.636 Å: the diketonate plane···Ph1 distance). The newly obtained circular lanthanide(III) helicate exists as single and homochiral diastereomers in solution (LnIII4- RRRR and LnIII4- SSSS), exhibiting circularly dichroism (CD) and circularly polarized luminescence (CPL). Conversely, the circular helicate favors the heterochiral arrangement (i.e., LnIII4- RRRR/LnIII4- SSSS).

Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts.

Recently, circularly polarized luminescence (CPL)-active systems have become a very hot and interesting subject in chirality- and optics-related areas. The CPL-active systems are usually available by two approaches: covalently combining a luminescent centre to chiral motif or associating the guest of luminescent probe to a chiral host. However, all the chiral components in CPL materials were organic, although the luminescent components were alternatively organics or inorganics. Herein, the first totally inorganic CPL-active system by "luminescent guest-chiral host" strategy is proposed. Luminescent sub-10 nm lanthanide oxides (Eu2 O3 or Tb2 O3 ) nanoparticles (guests) were encapsulated into chiral non-helical SiO2 nanofibres (host) through calcination of chiral SiO2 hybrid nanofibres, trapping Eu3+ (or Tb3+ ). These lanthanide oxides display circular dichroism (CD) optical activity in the ultraviolet wavelength and CPL signals around at 615 nm for Eu3+ and 545 nm for Tb3+ . This work has implications for inorganic-based CPL-active systems by incorporation of various luminescent guests within chiral inorganic hosts.

Terarylenes as Photoactivatable Hydride Donors.

Terarylene frameworks containing benzothiazole as a photoprecursor of hydride donors are presented. We here report on two new scaffolds along with their photoreactivity in solution. Through use of selected external oxidants, the photogeneration of hydride donors is monitored using UV-visible, NMR, and TEM methods. As a proof-of-concept, photogeneration of hydride in the presence of Ag+ gave rise to the formation of Ag nanoparticles.