Structure and Chiroptical Properties of Anthra[1,2-a]anthracene-1-yl Dimers as New Biaryls.

Dimers of anthra[1,2-a]anthracene-1-yl units and its mesityl derivative were synthesized by Ni(0)-mediated coupling of the corresponding chloro derivatives as new biaryls. The X-ray analysis and DFT calculations revealed that two polycyclic aromatic units with nonplanar deformations took a twisted conformation about the single bond as a chiral axis. Enantiomers of the nonsubstituted compound were resolved by chiral HPLC, and the enantiopure samples showed intense Cotton effects at 321 nm in the circular dichroism (CD) spectra and emission bands at 449 nm in the circularly polarized luminescence (CPL) spectra with dissymmetry factor of |glum| 3.6×10-3. The absolute stereochemistry of this biaryl was determined by the theoretical calculation of CD spectrum by the time-dependent DFT method. The barrier to enantiomerization was determined to be 108 kJ mol-1 at 298 K. The dynamic process proceeded via a stepwise mechanism involving the helical inversion of each aromatic unit and the rotation about the biaryl axis as analyzed by the DFT calculations.

Inversion of Diaza[5]Helicenes Through an N-N Bond Breaking Pathway.

1,1',10,10'-Biphenothiazine and its S,S,S',S'-tetroxide are diaza[5]helicenes with N-N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N-N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N-N bond by modification of S to SO2 at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1',10,10'-Biphenothiazine S,S,S',S'-tetroxide was highly resistant to acid-mediated N-N bond breaking and racemization under acidic conditions.

High-Pressure Synthesis of a High-Pressure Phase of MnN Having NiAs-Type Structure.

A novel high-pressure phase of manganese mononitride, NiAs-type MnN, was successfully synthesized through a pressure-induced phase transition from a tetragonal distorted NaCl-type MnN at pressures above approximately 55 GPa. High-pressure experiments, including starting material preparation, were conducted using a laser-heated diamond anvil cell. This result is the first example of a nitride with a structural phase transition from the distorted NaCl-type to the NiAs-type structure. Upon decompression after the phase transition to NiAs-type structure, the NiAs-type MnN underwent a structural change to the distorted NaCl-type phase, indicating the phase transition was reversible. NiAs-type MnN has a higher density and bulk modulus in comparison to the distorted NaCl-type one. The phase transition pressure of MnN is lower than that of oxides, such as FeO and MnO, which show a structural phase transition from a NaCl-type to a NiAs-type structure. It is suggested that this is due to the lattice distortion caused by antiferromagnetic ordering.

Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness.

Invited for the cover of this issue are Masashi Hasegawa and co-workers at Kitasto University and Kyoto Prefectural University. The image depicts the reported multiply twisted chiral macrocycles as objects in a kaleidoscope. Read the full text of the article at 10.1002/chem.202202218.

Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness.

Chiral macrocyclic dimers, trimers, and tetramers composed of paraphenylene and tethered binaphthyl were synthesized, and their molecular structures and chiroptical properties were investigated. X-ray analysis and theoretical calculations revealed that multiple twisted molecular structures - dimers, trimers, and tetramers - adopt figure-of-eight, Möbius triangle, and concave rectangle structures, respectively. These homologues have large ϵ values in their UV-vis absorption spectra because of the π-conjugation of the naphthalene-phenylene-naphthalene frameworks. Owing to the shape-persistent ring structure and tethering with -OCH2 CH2 O-, high fluorescence quantum yields and a relatively high dissymmetry factor gCPL in circularly polarized luminescence (CPL) spectra were achieved. This results in CPL brightness (BCPL ) of over 100, which is greater than that of the conventional organic CPL dye.

Oxidation of an Internal-Edge-Substituted [5]Helicene-Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence.

Small chiral organic molecules with CD properties are in high demanded due to their potential use in promising electronic and biological applications. Herein, we reveal a system in which the oxidation of a phosphino group to the corresponding phosphine oxide on the inner rim of a helicene derivative induces a CPL response. Laterally π-extended 7,8-dihydro[5]helicenes bearing phosphine and phosphine oxide groups on their inner helical rims (i. e., the C1 position) were synthesized, and their helical structures were unambiguously determined by X-ray crystallography. The photophysical (UV/visible and emission) and chiroptical properties of these compounds were investigated in various solvents. Despite their structural similarities, phosphine oxide showed a significantly better CPL response than phosphine, with a high dissymmetry factor for emission (|glum |=(1.3-1.9)×10-3 ) that can be attributed to structural changes in the interior of the helicene helix.

Oxidation of an Internal-Edge-Substituted [5]Helicene-Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence.

Invited for the cover of this issue are the groups of Kazuteru Usui and Satoru Karasawa at Showa Pharmaceutical University, and Yoshitane Imai at Kindai University. The image depicts how a phosphine-oxide-bearing helicene exhibits markedly enhanced CPL response in the excited state compared with that of one with a corresponding phosphine. Read the full text of the article at 10.1002/chem.202202922.

Small Figure-Eight Luminophores: Double-Twisted Tethered Cyclic Binaphthyls Boost Circularly Polarized Luminescence.

Double-twisted cyclic binaphthyls, in which two naphthalenes are tethered by -O(CH2 )n O- linkage (n=1-3), have been synthesized. X-ray analyses and DFT calculations revealed a tightly constrained stereogenic figure-eight geometry. Tethering of two naphthalenes by short linkage forces a small dihedral angle, and the cyclic binaphthyls with short tether (n=1, 2) exhibit remarkable boosting of the glum value (1.0-1.6×10-2 ) in circularly polarized luminescence (CPL) and unusual glum /gabs ratios (0.93-1.3). These experimental high |glum | values are in accord with the results of excited state TD-DFT calculations, which show transannular interactions and that consequent extensive delocalization occurs throughout the figure-eight π-core. As a result, the present figure-eight luminophore promote the elongation of the magnetic transition dipole moment that results in significant increases in glum values.

Small Figure-Eight Luminophores: Double-Twisted Tethered Cyclic Binaphthyls Boost Circularly Polarized Luminescence.

Invited for the cover of this issue are Masashi Hasegawa, Yoshitane Imai and co-workers at Kitasato University and Kindai University. The image depicts the reported figure-eight molecule as an M. C. Escher-inspired 'impossible object'. Read the full text of the article at 10.1002/chem.202005320.

Circularly Polarized Luminescence of a Stereogenic Curved Paraphenylene Anchoring a Chiral Binaphthyl in Solution and Solid State.

Invited for the cover of this issue are Masashi Hasegawa, Yoshitane Imai, Yasuhiro Mazaki and co-workers at Kitasato University, Kindai University and Osaka University. The image depicts a stereogenic twisted cycloparaphenylene that exhibits circularly polarized luminescence in a polymethyl methacrylate thin film. Read the full text of the article at 10.1002/chem.202004283.

Circularly Polarized Luminescence of a Stereogenic Curved Paraphenylene Anchoring a Chiral Binaphthyl in Solution and Solid State.

A curved stereogenic [6]paraphenylene ([6]PP), anchoring a chiral binaphthyl scaffold at 7,7'-positions, was prepared and investigated for its properties as a solid-state circularly polarized luminescence (CPL) dye. X-ray analysis revealed a helically twisted structure of PP units induced by axial chirality of binaphthyl framework. The curved [6]PP exhibits fluorescence in powder and polymethyl methacrylate (PMMA) film as well as solution. A significant increase in quantum yield was observed for a non-fluid PMMA film owing the suppression of the molecular motion. The gCPL values of the dye in solution and as PMMA film were almost the same (4.3-4.4×10-3 ) and lager than that in powder. TD-DFT calculations in the excited state suggest that the exciton can be delocalized into a twisted PP unit to produce a larger magnetic transition dipole moment.

Helical Oligophenylene Linked with [2.2]Paracyclophane: Stereogenic π-Conjugated Dye for Highly Emissive Chiroptical Properties.

A stereogenic π-system based on dimer (2) and trimer (3) of [2.2]paracyclophane (PC) and biphenyl was prepared and its structural, photophysical, and chiroptical properties were investigated. X-ray analysis revealed that the quaterphenyl moieties in 2 adopt a double helical structure anchoring [2.2]PC from both sides. Furthermore, 3 forms a isosceles triangle structure with a large chiral cavity. A homodesmotic reaction using DFT calculations revealed that 2 has a larger strain energy than 3 owing to its highly twisted phenylene linkers. Electronic and circular dichroic (CD) spectra were recorded in CH2 Cl2 solution. The spectra of both 2 and 3 are similar, and their longest absorption band accompanying a remarkable Cotton effect is attributed to the transition from HOMO to LUMO, which is delocalized to the quaterphenyl moiety. These compounds exhibit fairly high fluorescence quantum yields (ϕ=0.70-0.83) and moderate dissymmetry factor (|gCPL |=1.6×10-3 ) in circularly polarized luminescence (CPL).

Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions.

McMurry coupling is one of the most useful and convenient tools for the preparation of π-conjugated molecules. However, for the synthesis of strained macrocycles containing ethynylene linkages, reduction of ethynylene to vinylene linkage sometimes took place. Especially, for the synthesis of macrocyclic π-extended thiophene hexamers using McMurry coupling of dialdehyde 1 composed of three thienylene, two ethynylene, and two formyl groups, reduction of ethynylenes to vinylenes often takes place to produce unique products in a one-pot procedure, depending on very small steric and electronic effects such as reaction temperature, amounts of titanium reagent, and substituents of thiophene hexamers. The attractive structures and functional properties of reduced thiophene hexamers have been determined using X-ray analysis and OFET measurements.

Crystal and Electronic Structure of U7Te12-Type Tungsten Nitride Synthesized under High Pressure.

Tungsten nitride continues to drive fundamental interests because of its potential as a functional compound, which combines features such as high hardness together with thermal, chemical, and wear resistance. Here, we report a novel tungsten nitride phase synthesized from MoC-type WN0.6 and molecular nitrogen after laser irradiation at P = 70 GPa in a diamond anvil cell. This novel phase is quenchable at ambient pressure and determined to be U7Te12-type tungsten nitride and crystallizes in the hexagonal space group (P6) having lattice parameters of a = 8.2398(3) Å, c = 2.94948(14) Å, and V = 173.423(13) Å3. Tungsten atoms are coordinated to eight and nine nitrogen atoms, higher than previously reported tungsten nitrides. The bulk modulus is determined to be K0 = 312 (5) GPa (K0' = 4.0 fixed), and DFT calculations predict that U7Te12-type W7N12 has a metallic nature.

Pressure-Tunable Crystal Structure and Magnetic Transition Temperature of the Nowotny Chimney-Ladder CrGeγ Phase.

A Nowotny chimney-ladder (NCL) chromium germanide (CrGeγ) with varying compositions has been synthesized under high pressure. Crystal structure parameters of the NCL CrGeγ have been calculated by Le Bail refinement based on the superspace group. The refined γ of CrGeγ increases with the synthesis pressure, indicating an increasing Ge content. The NCL CrGeγ phases are ferromagnetic at T = 2 K regardless of their composition, and the magnetic transition temperature (TC) increases when the γ becomes higher. It is noteworthy that CrGe1.763 and CrGe1.774 synthesized at P = 10 and 14 GPa have magnetic transition temperatures of T = 295 and 333 K above room temperature, respectively. Surprisingly, the magnetic transition temperature has changed by ΔTC = 270 K, although the γ values of the raw material and the sample synthesized at P = 14 GPa differ by only Δγ = 0.05, corresponding to an atomic concentration of 0.62 atom %. The synthesis pressure acts as an essential parameter in tuning the composition of the NCL phase. Accordingly, the high-pressure synthesis may significantly control several physical characteristics of NCL phases by utilizing compositional and structural modulation.

Crystal and Electronic Structures of MoSi2-Type CrGe2 Synthesized under High Pressure.

Chromium germanides, namely, Nowotny chimney-ladder-phase CrGe1.77 and MoSi2-type CrGe2, were synthesized above 15 GPa or more via laser heating using a diamond anvil cell (LHDAC). MoSi2-type CrGe2, which is the most Ge-rich compound in the Cr-Ge system, crystallizes in the tetragonal structure with a space group of I4/mmm (no. 139) and lattice parameters of a = 3.24919(6) Å and c = 8.0523(3) Å and is isostructural with MoSi2. MoSi2-type CrGe2 has a deep pseudogap caused by the splitting of 3d orbitals with Cr, as evidenced by ab initio calculation. In this article, we have succeeded in synthesizing a binary compound between transition-metal and metalloid elements for the first time at high pressures above 10 GPa using the LHDAC. This pathway opens the possibility to explore more compounds in this system and may provide new insights into the fundamental interaction between these two elements.

Phase relations and thermoelasticity of magnesium silicide at high pressure and temperature.

Within the exploration of sustainable and functional materials, narrow bandgap magnesium silicide semiconductors have gained growing interest. Intriguingly, squeezing silicides to extreme pressures and exposing them to non-ambient temperatures proves fruitful to study the structural behavior, tune the electronic structure, or discover novel phases. Herein, structural changes and thermoelastic characteristics of magnesium silicides were probed with synchrotron x-ray diffraction techniques using the laser-heated diamond anvil cell and large volume press at high pressure and temperature and temperature-dependent synchrotron powder diffraction. Probing the ambient phase of Mg2Si (anti-CaF2-type Mg2Si, space group: Fm3¯m) at static pressures of giga-Pascals possibly unveiled the transformation to metastable orthorhombic anti-PbCl2-type Mg2Si (Pnma). Interestingly, heating under pressures introduced the decomposition of Mg2Si to hexagonal Mg9Si5 (P63) and minor Mg. Using equations of state (EoS), which relate pressure to volume, the bulk moduli of anti-CaF2-type Mg2Si, anti-PbCl2-type Mg2Si, and Mg9Si5 were determined to be B0 = 47(2) GPa, B0 ≈ 72(5) GPa, and B0 = 58(3) GPa, respectively. Employing a high-temperature EoS to the P-V-T data of anti-CaF2-type Mg2Si provided its thermoelastic parameters: BT0 = 46(3) GPa, B'T0 = 6.1(8), and (∂BT0/∂T)P = -0.013(4) GPa K-1. At atmospheric pressure, anti-CaF2-type Mg2Si kept stable at T = 133-723 K, whereas Mg9Si5 transformed to anti-CaF2-type Mg2Si and Si above T ≥ 530 K. This temperature stability may indicate the potential of Mg9Si5 as a mid-temperature thermoelectric material, as suggested from previous first-principles calculations. Within this realm, thermal models were applied, yielding thermal expansion coefficients of both silicides together with estimations of their Grüneisen parameter and Debye temperature.

Dinuclear Triple-Stranded Helicates Composed of Tetradentate Ligands with Aluminum(III) Chromophores: Optical Resolution and Multi-color Circularly Polarized Luminescence Properties.

New chiroptical chromophores, dinuclear triple-stranded helicates, composed of tetradentate ligands with aluminum(III) ions, are described. These are synthesized in two steps using inexpensive pyrrole derivatives, hydrazine, and aluminum chloride. These molecular architectures (ALPHY) show multi-color (cyan, yellow, and orange) photoluminescence in solution and in the solid-state, which depends on the substituents of the ligands. The photoluminescence quantum yields of helicates were up to 54 %. The right-handed (P) and left-handed (M) helicates are so stable that they do not undergo racemization in some solvents and are mirror images according to circular dichroism and circularly polarized luminescence (CPL) with an absolute luminescence dissymmetry factor (glum ) of up to the 10-3 order. Mixing the different helicates produces white-light emission with CPL characters. This study offers a glimpse into the potential applications of chromophores with diverse photophysical properties.

Reversible Color and Shape Changes of Nanostructured Fibers of a Macrocyclic π-Extended Thiophene Hexamer Promoted by Adsorption and Desorption of Organic Vapor.

A phenyl-substituted macrocyclic π-extended thiophene hexamer 1, composed of four thienylene-ethynylene and two thienylene-vinylene units, has a solid-state structure in which π-π, CH-π, and van der Waals interactions occur. Slow addition of acetone to a solution of 1 in CS2 produces a yellow nanostructured fiber 1-A containing a 1:1.5:1 ratio of 1, acetone, and CS2. Over a 2 min period at 25 °C, 1-A gradually changes to an orange fiber 1-B containing a 1:0.5:1 ratio of 1, acetone, and CS2. On exposure to acetone vapor, 1-B regenerates 1-A (vapochromism), and removal of all solvents from 1-A and 1-B generates a red-orange fiber 1-C, which upon brief immersion in acetone/CS2 produces 1-A. Furthermore, 1-C is converted to orange yellow fiber 1-D upon exposure to acetone vapor for 1 s at 25 °C. Analysis of the horizontal and vertical profiles of the X-ray diffraction (XRD) patterns shows that removal of solvent from 1-A reversibly creates 1-B in conjunction with a shape and size change along with arching.

Thermal Expansion of Incompressible U2S3-Type Nb2N3 Synthesized in a Diamond Anvil Cell.

A novel niobium nitride, U2S3-type Nb2N3, has been successfully synthesized by nitridation of δ-NbN above approximately 30 GPa in a laser-heated diamond anvil cell. Nb2N3 crystallizes in the same orthorhombic structure (space group: Pnma) as η-Ta2N3. Nb2N3 consists of regular-shaped polyhedra, and the bulk modulus has been determined to K0 = 300(2) GPa. The low-temperature X-ray diffraction measurements have been successfully conducted for the tiny novel Nb2N3 between 297.7(5) and 106.3(3) K under ambient pressure. Nb2N3 shows no structural phase transition down to 106.3(3) K, and investigation of the linear thermal expansion coefficients yields αa = 3.36(9) × 10-6 K-1, αb = 5.39(10) × 10-6 K-1, αc = 6.77(15) × 10-6 K-1, respectively. Our study reveals that the incompressible novel nitride shows low thermal expansion behavior, which offers new insights for the development of functional nitrides and their crystal chemistry.