Of the five possible indenofluorene regioisomers, examples of a fully conjugated indeno[1,2-a]fluorene scaffold have so far remained elusive. This work reports the preparation and characterization of 7,12-dimesitylindeno[1,2-a]fluorene as a highly reactive species. Experimental and computational data support the notion of a molecule with pronounced diradical character that exists in a triplet ground state. As such, both NICS and ACID calculations suggest that the indeno[1,2-a]fluorene scaffold is weakly Baird aromatic. Reduction of the unstable red solid with Cs metal produces the dianion of the title compound, from which single crystals could be obtained and X-ray data acquired, thus fully corroborating the proposed indeno[1,2-a]fluorene hydrocarbon core.

We report the unprecedented synthesis of onehanded helical spiro-conjugated ladder polymers with welldefined primary and secondary structures, in which the spirolinked dibenzo [a,h]anthracene fluorophores are arranged in a one-handed twisting direction, through quantitative and chemoselective acid-promoted intramolecular cyclizations of random-coil precursor polymers composed of chiral 1,1'spirobiindane and achiral bis[2-(4-alkoxyphenyl)ethynyl]phenylene units. Intense circular dichroism (CD) and circularly polarized luminescence (CPL) were observed, whereas the precursor polymers exhibited negligible CD and CPL activities. The introduction of 2,6-dimethyl substituents on the 4alkoxyphenylethynyl pendants is of key importance for this simple, quantitative, and chemoselective cyclization. This strategy is applicable to the defect-free precise synthesis of other varieties of fully p-conjugated molecules and coplanar ladder polymers that have not been achieved before.

Separating substances by their chirality faces great challenges as well as opportunities in chemistry and biology. In this study, we propose an all-optical solution for passive sorting of chiral objects using chirality-dependent lateral optical forces induced by judiciously interfered fields. First, we investigate the optical forces when the chiral objects are situated in the interference field formed by two plane waves with arbitrary polarization states. When the plane waves are either linearly or circularly polarized, nonzero lateral forces are found at the particle's trapping positions, making such sideways motions observable. Although the lateral forces have different magnitudes on particles with different chirality, their directions are the same for opposite handedness particles, rendering it difficult to separate the chiral particles. We further solve the sorting problem by investigating more complicated polarization states. Finally, we achieve the chiral-selective separation by illuminating only one beam toward the chiral substance situated at an interface between two media, taking advantage of the native interference between the incident and reflective beams at the interface. Our study provides a robust and insightful approach to sort chiral substances and biomolecules with plausible optical setups.

Four iodobismuthates, LiBiI4·5H2O (1), MgBi2I8·8H2O (2), MnBi2I8·8H2O (3), and KBiI4·H2O (4), were prepared by a facile solution route and revealed thermal stability in air up to 120 °C. Crystal structures of compounds 1-4 were solved by a single crystal X-ray diffraction method. 1: space group C2/c, a = 12.535(2), b = 16.0294(18), c = 7.6214(9) Å, β = 107.189(11)°, Z = 4, R = 0.029. 2: space group P21/c, a = 7.559(2), b = 13.1225(15), c = 13.927(4) Å, β = 97.14(3)°, Z = 2, R = 0.031. 3: space group P21/c, a = 7.606(3), b = 13.137(3), c = 14.026(5) Å, β = 97.14(3)°, Z = 2, R = 0.056. 4: space group P21/n, a = 7.9050(16), b = 7.7718(16), c = 18.233(4) Å, β = 97.45(3)°, Z = 4, R = 0.043. All solid state structures feature one-dimensional (BiI4)(-) anionic chains built of [BiI6] octahedra that share two opposite edges in such a fashion that two iodine atoms in cis-positions remain terminal. The calculated electronic structures and observed optical properties confirmed that compounds 1-4 are semiconductors with direct band gaps of 1.70-1.76 eV, which correspond to their intense red color. It was shown that the cations do not affect the optical properties, and the optical absorption is primarily associated with the charge transfer from the I 5p orbitals at the top of the valence band to the Bi 6p orbitals at the bottom of the conduction band. Based on their properties and facile synthesis, the title compounds are proposed as promising light-harvesting materials for all-solid solar cells.

An X-ray diffraction study of [6]cycloparaphenylene (1), crystallized under solvent-free conditions, revealed a unique solid state structure with tight packing of individual molecules that minimizes empty internal space. The controlled chemical reduction of this highly strained nanohoop with Group 1 metals resulted in the first isolation and structural characterization of its mono- and dianions, allowing for the evaluation of core transformations for the series ranging from 10 to 11- and 12-.

Incorporation of a five‐membered ring into a helicene framework disrupts aromatic conjugation and provides a site for selective deprotonation. The deprotonation creates an anionic cyclopentadienyl unit, switches on conjugation, leads to a >200 nm red‐shift in the absorbance spectrum and injects a charge into a helical conjugated π‐system without injecting a spin. Structural consequences of deprotonation were revealed via analysis of a monoanionic helicene co‐crystallized with {K+(18‐crown‐6)(THF)} and {Cs+2(18‐crown‐6)3}. UV/Vis‐monitoring of these systems shows a time‐dependent formation of mono‐ and dianionic species, and the latter was isolated and crystallographically characterized. The ability of the twisted helicene frame to delocalize the negative charge was probed as a perturbation of aromaticity using NICS scans. Relief of strain, avoidance of antiaromaticity, and increase in charge delocalization assist in the additional dehydrogenative ring closures that yield a new planarized decacyclic dianion.

The reduced and oxidized states of an open-shell diindeno[b,i]anthracene (DIAn) derivative have been investigated by experimental and theoretical techniques. As a result of moderate biradical character and the ability of cyclopenta-fused scaffolds to stabilize both positive and negative charges, DIAn exhibits rich redox chemistry with four observable and isolable charged states. Structural and electronic properties of the DIAn system are brought to light by UV-vis-NIR and Raman spectroelectrochemical measurements. Aromatization of the diindeno-fused anthracene core upon successive single-electron injections is revealed through single-crystal X-ray diffraction of radical anion and dianion salts. We present a rare case where the pseudoaromatic/quinoidal ground state of a neutral biradical polycyclic hydrocarbon leads to a stable cascade of five redox states. Our detailed investigation of the transformation of molecular structure along all four redox events provides a clearer understanding of the nature of charge carriers in ambipolar organic field-effect transistors.

Phenylenediammonium polyiodobismuthate­(III), [PDA­(BiI4)2·​I2] (PDA = phenyl­ene­diam­monium, [NH3­C6H4­NH3]2+), represents a new hybrid halometallate synthesized in a form of black well-shaped crystals by a facile reaction in aqueous solution of HI containing dissolved I2. It crystallizes in triclinic space group P1̅ with the unit cell parameters a = 7.761(1) Å, b = 9.259(1) Å, c = 9.689(1) Å, α = 95.68(3)°, β = 103.19(3)°, γ = 93.56(3)°, and Z = 1. Its crystal structure comprises three levels of organization discriminated by a type of chemical bonding. The first level is provided by covalently bonded [BiI6] octahedra linked into [BiI4]∞ – one-dimensional anionic chains; the second level features secondary bonds between the chains and I2 bridging molecules, whereas the third level is specified by the weak hydrogen N–H···I bonds involving a diammonium cation and I···I intermolecular interactions that additionally link anionic chains. Altogether, these three interaction types ensure the formation of a complex pseudo-three-dimensional crystal structure. According to optical absorption study, [PDA­(BiI4)2·​I2] is a semiconductor with the band gap of 1.45 eV.