Crystal and mol-ecular structure of 2-methyl-1,4-phenyl-ene bis-(3,5-di-bromo-benzoate).

The aryl diester compound, 2-methyl-1,4-phenyl-ene bis-(3,5-di-bromo-benzoate), CHBrO, was synthesized by esterification of methyl hydro-quinone with 3,5-di-bromo-benzoic acid. A crystalline sample was obtained by cooling a sample of the melt (m.p.

Influence of donor point modifications on the assembly of chalcogen-bonded organic frameworks.

Incremental, single-atom substitutions of Se-based chalcogen bond (Ch-bond) donors with stronger donating Te centers were implemented in two new triptycene tris(1,2,5-chalcogenadiazole) tectons. The appreciably more favorable Ch-bonding ability of the Te-based donors promotes assembly of low-density networks and more stable Ch-bonded organic frameworks (ChOFs).

2,2'-{(1,1')-[Ethane-1,2-diylbis(aza-nylyl-idene)]bis-(methanylyl-idene)}bis-(4-iodo-phenol).

The title compound, CHINO, a di-iodo-Schiff base, crystallizes in space group with one mol-ecule per asymmetric unit. The mol-ecular structure reveals two intra-molecular O-H⋯N hydrogen bonds that give the mol-ecule a twisted structure with non-coplanar rings. In the crystal structure, the mol-ecular packing is stabilized by π-π stacking, hydrogen- and halogen-bonding (C-H⋯I; O⋯I) inter-actions.

A Porous Chalcogen-Bonded Organic Framework.

The manner of bonding between constituent atoms or molecules invariably influences the properties of materials. Perhaps no material family is more emblematic of this than porous frameworks, wherein the namesake modes of connectivity give rise to discrete subclasses with unique collections of properties. However, established framework classes often display offsetting advantages and disadvantages for a given application.

Configurational Lability at Tetrahedral Phosphorus: syn/anti-Isomerization of a P-Stereogenic Phosphiranium Cation by Intramolecular Epimerization at Phosphorus.

Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH CHPh][OTf] (Mes*=2,4,6-(t-Bu) C H ) occurred under mild conditions at 60 °C in CD Cl , resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu ][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C Cl O ) ) followed by chromatography on silica removed [NBu ][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH CHPh][Δ-TRISPHAT]⋅x[NBu ][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C.

Crystal structure of 1,2-bis-(3,5-di-fluoro-phen-yl)ethane-1,2-dione.

The title compound, CHFO, crystallizes with half of a mol-ecule per asymmetric unit and exhibits bond lengths and angles typical of α-diketones. A network of C-H⋯F contacts and π-π stacking inter-actions is observed within the structure.

Carborane Guests for Cucurbit[7]uril Facilitate Strong Binding and On-Demand Removal.

High-affinity guests have been reported for the macrocyclic host cucurbit[7]uril (CB[7]), enabling widespread applications, but hindering CB[7] materials from being returned to their guest-free state for reuse. Here, we present polyhedral boron clusters (carboranes) as strongly binding, yet easily removable, guests for CB[7]. Aided by a Pd-catalyzed coupling of an azide anion, we prepared boron-functionalized 9-amino--carborane that binds to CB[7] with a ≈ 10 M.

Correlation of Structure with Crystalline to Amorphous Phase Transitions of 1,3,6-Substituted Fulvene-Derived Molecular Glasses.

An investigation into the crystalline to amorphous phase transitions of prepared 1,3,6-substituted pentafulvenes showed the expected reversible heated melt and cooling recrystallization in only a few examples. Systematic incorporation of bulky substituents at the 6-position of the fulvene ring led to the nonreversible thermal behavior, rendering phases that were locked into glassy, vitrified states. These molecular glasses produced physically translucent and amorphous features with glass transition temperatures in the range of 61-77 °C, comparable with high-strength plastics such as polyethylene terephthalate.

Diastereoselective Synthesis of P-Stereogenic Secondary Phosphine Oxides (SPOs) Bearing a Chiral Substituent by Ring Opening of (+)-Limonene Oxide with Primary Phosphido Nucleophiles.

Kinetic separation of the commercially available /-(+)-limonene oxide mixture by ring opening with primary phosphido nucleophiles LiPHR (R = ferrocenyl, Ph, Cy, -Bu, Mes* (Mes* = 2,4,6-(-Bu)CH)), followed by treatment with aqueous NHCl and HO, gave unreacted -(+)-limonene oxide and diastereoenriched mixtures of the secondary phosphine oxides (SPOs) PHR(-(+)-Lim-OH)(O), which could be separated by chromatography and/or recrystallization. This one-pot synthesis uses a cheap chiral material and commercially available primary phosphines to control the configuration of the new P-stereogenic SPOs, which are potentially useful as ligands for metal complexes in asymmetric catalysis.

Luminescence of Lanthanide Complexes with Perfluorinated Alkoxide Ligands.

Four groups of rare-earth complexes, comprising 11 new compounds, with fluorinated O-donor ligands ([K(THF)][Ln(OCF)(THF)] (; Ln = Ce, Nd), [K](THF)[Ln(OCF)(THF)] (; Ln = Eu, Gd, Dy), [K(THF)][Ln(pin)(THF)] (; Ln = Ce, Nd), and [K(THF)][Ln(pin)(THF)] (; Ln = Eu, Gd, Dy, Y) have been synthesized and characterized. Single-crystal X-ray diffraction data were collected for all compounds except . Species , , and are uncommon examples of six-coordinate (Eu, Gd, Dy, and Y) and seven-coordinate (Ce and Nd) Ln centers in all-O-donor environments.

Crystal structures of 6-cyclo-propyl-1,3-diphenylfulvene and 6-(2,3-di-meth-oxy-naphth-yl)-1,3-di-phenylfulvene.

The title compounds, 6-cyclo-propyl-1,3-diphenylfulvene, CH, [systematic name: 5-(cyclo-propyl-methyl-idene)-1,3-di-phen-yl-cyclo-penta-1,3-diene], , and 6-(2,3-di-meth-oxy-naphth-yl)-1,3-diphenylfulvene, CHO, {systematic name: 5-[(3,4-di-meth-oxy-naphthalen-2-yl)methyl-idene]-1,3-di-phenyl-cyclo-penta-1,3-di-ene}, , were prepared from 1,3-di-phenyl-cyclo-penta-diene, pyrrolidine, and the corresponding aldehydes in an ethano-lic solution. Each structure crystallizes with one mol-ecule per asymmetric unit and exhibits the alternating short and long bond lengths typical of fulvenes. A network of C-H⋯C ring inter-actions as well as C-H⋯O inter-actions is observed, resulting in the compact packing found in each structure.

A molecular boron cluster-based chromophore with dual emission.

Bromination of the luminescent borane, anti-B18H22, via electrophilic substitution using AlCl3 and Br2, yields the monosubstituted derivative 4-Br-anti-B18H21 as an air-stable crystalline solid. In contrast to the unsubstituted parent compound, 4-Br-anti-B18H21 possesses dual emission upon excitation with UV light and exhibits fluorescence at 410 nm and phosphorescence at 503 nm, with Φtotal = 0.07 in oxygen-free cyclohexane.

Syntheses, crystal structures and Hirshfeld surface analyses of (3a,4,7,7a)-2-(perfluoro-pyridin-4-yl)-3a,4,7,7a-tetra-hydro-4,7-methano-iso-indole-1,3-dione and (3a,4,7,7a)-2-[(perfluoro-pyridin-4-yl)-oxy]-3a,4,7,7a-tetra-hydro-4,7-methano-iso-indole-1,3-dione.

The syntheses and crystal structures of the title compounds, CHFNO and CHFNO, are reported. In each crystal, the packing is driven by C-H⋯F inter-tactions, along with a variety of C-H⋯O, C-O⋯π, and C-F⋯π contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing: they showed that the largest contributions to the surface contacts arise from H⋯F/F⋯H inter-actions, followed by H⋯H and O⋯H/H⋯O.

Crystal structures and Hirshfeld surface analysis of a series of 4--aryl-perfluoro-pyridines.

Five new crystal structures of perfluoro-pyridine substituted in the 4-position with phen-oxy, 4-bromo-phen-oxy, naphthalen-2-yl-oxy, 6-bromo-naphthalen-2-yl-oxy, and 4,4'-biphen-oxy are reported, 2,3,5,6-tetra-fluoro-4-phen-oxy-pyridine, CHFNO (), 4-(4-bromo-phen-oxy)-2,3,5,6-tetra-fluoro-pyridine, CHBrFNO (), 2,3,5,6-tetra-fluoro-4-[(naphthalen-2-yl)-oxy]pyridine, CHFNO (), 4-[(6-bromo-naphthalen-2-yl)-oxy]-2,3,5,6-tetra-fluoropyridine, CHBrFNO (), and 2,2'-bis-[(perfluoro-pyridin-4-yl)-oxy]-1,1'-biphenyl, CHFNO (). The dihedral angles between the aromatic ring systems in - are 78.74 (8), 56.

Crystal structures of a series of 6-aryl-1,3-diphenyl-fulvenes.

The synthesis and crystal structures of a series of 6-aryl-fuvlenes (fulvene is 5-methyl-idene-cyclo-penta-1,3-diene) with varying methyl-ation patterns on the 6-phenyl substituent are reported, namely 6-(3-methyl-phen-yl)-1,3-di-phenyl-fulvene (CH), 6-(4-methyl-phen-yl)-1,3-di-phenyl-fulvene (CH), 6-mesityl-3-di-phenyl-fulvene (CH) and 6-(2,3,4,5,6-penta-methyl-phen-yl)-1,3-di-phenyl-fulvene (CH). The bond lengths are typical of those observed in related fulvenes. A network of C-H⋯π ring inter-actions consolidates the packing in each structure.

Synthesis of reactive 1,3-diphenyl-6-aryl-substituted fulvene chromophores.

This data article describes a detailed synthetic strategy and experimental data for the synthesis of brominated fulvene chromophores as reactive precursors/monomers for conjugated organic materials. Metal-mediated coupling reactions of brominated fulvenes would result in conjugated small molecules or polymers that would find application as organic light emitting diodes (OLEDs) and photovoltaic (PV) applications.

Coordination complexes of chromium(0) with a series of 1,3-diphenyl-6-aryl-fulvenes.

The synthesis and structural properties of a series of chromium tricarbonyl 'piano-stool' complexes bearing substituted penta-fulvene ligands were studied. The complexes, tricarbon-yl(1,3,6-tri-phenyl-fulvene)chromium(0) benz-ene hemisolvate, [Cr(CH)(CO)]·0.5CH (), tricarbon-yl[1,3-di-phen-yl-6-(3-vinyl-phen-yl)fulvene]chromium(0), [Cr(CH)(CO)] (), and tricarbon-yl[1,3-diphenyl-6-(pyren-1-yl)fulvene]chromium(0), [Cr(CH)(CO)] (), each have a distorted octa-hedral geometry, with the fulvene coordinated in a π-η:π-ηπ-η fashion.

Crystal structure of chlorido-(dimethyl sulfoxide-κ)bis-[4-(pyridin-2-yl)benzaldehyde-κ,]iridium(III) aceto-nitrile monosolvate.

The title compound, [IrCl(CHNO){(CH)SO}]·HCCN or [IrCl(fppy)(DMSO)]·HCCN [where fppy is 4-(pyridin-2-yl)benzaldehyde and DMSO is dimethyl sulfoxide], is a mononuclear iridium(III) complex including two fppy ligands, a sulfur-coordinating DMSO ligand, and one terminal chloride ligand that define a distorted octa-hedral coordination sphere. The complex crystallizes from 1:1 DMSO-aceto-nitrile as an aceto-nitrile solvate. In the crystal, weak C-H⋯O and C-H⋯N hydrogen-bonding inter-actions between adjacent complexes and between the aceto-nitrile solvent and the complex consolidate the packing.

Synthesis, Electrochemical Characterization, and Linear Free Energy Relationship of 1,3-Diphenyl-6-alkyl/arylfulvenes.

A series of 1,3-diphenyl-6-alkyl/arylfulvenes was prepared, and the electrochemical properties were investigated. The addition of phenyl groups about the fulvene raised the reduction potential and helped to stabilize the electrochemically generated radical anion. The addition of various functional groups onto the phenyl ring at the 6-position of 1,3,6-triphenylfulvene results in a linear free energy relationship between reduction potential and the Hammett substituent constant, σ.

First preparation of low band gap fulvene-modified polynorbornene via ring-opening metathesis polymerization.

New polymers containing intact pendant-fulvene moieties have been successfully prepared from 1,3-phenyl-6-norbornenylfulvene via ring-opening metathesis polymerization (ROMP). The prepared polyfulvenes have unique electrochemical and photophysical properties which make them interesting candidates for light harvesting materials.

3-(4-Bromo-phen-yl)cyclo-pent-2-en-1-one.

In the title compound, C11H9BrO, the cyclo-pentenone ring is almost planar with an r.m.s.

Synthesis of 1,3-diphenyl-6-alkyl/aryl-substituted fulvene chromophores: observation of π-π interactions in a 6-pyrene-substituted 1,3-diphenylfulvene.

The synthesis, structural, and electronic properties of nine 1,3-diphenyl-6-alkyl/aryl substituted pentafulvenes were studied. Pyrene ring π-π interactions were revealed from analysis of the experimental crystal packing of 1,3-diphenyl-6-(1-pyrene)fulvene and supporting DFT calculations. Photophysical properties derived from UV-vis and fluorescence emission measurements demonstrated tunable and low HOMO-LUMO band gaps for the series.

Synthesis, Structure, and Reactivity of 1,2-(1',1',2',2'-Tetramethyldisilane-1',2')carborane.

The novel strained compound 1,2-(1',1',2',2'-tetramethyldisilane-1',2')carborane (1) was synthesized by the reaction of 1,2-dilithiocarborane and dichlorotetramethyldisilane. Compound 1 was characterized by solution methods and its structure determined by single-crystal X-ray diffraction. In contrast to its organic analogue o-(disilanyl)phenylene, the reaction of 1 with ethanol leads to cleavage of a Si-C bond rather than a Si-Si bond.