: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

The 31 P NMR spectra of triethylphosphine oxide (Et 3 PO) undergoes a shift upon interaction in solution with adjacent molecules. The oxygen of Et 3 PO is a strong electron donor and readily forms acid-base complexes with electron acceptors, with a consequent downfield shift in the 31 P NMR spectrum (Δδ ab ). We find that the 31 P NMR spectrum also is shifted downfield appreciably by van der Waals (largery dispersion force) interactions with solvents (Δδ d )

Spectral shifts in acid-base chemistry. II: Van der Waals contributions to acceptor numbers

Polymorphism and solvatomorphism 2005

Reaction of CuI with bis(phenylthio)propane in a 1:1 ratio yields the two-dimensional coordination polymer [{Cu(μ2-I)2Cu}{μ-PhS(CH2)3SPh}2]n (1). The 2D-sheet structure of 1 is built up by dimeric Cu2I2 units, which are connected via four bridging 1,3-bis(phenylthio)propane ligands. In contrast, treatment of 2 equiv of CuI with 1,3-bis(phenylthio)propane in MeCN solution affords in a self-assembly reaction the strongly luminescent metal–organic 2D-coordination polymer [Cu4I4{μ-PhS(CH2)3Ph}2]n (2), in which cubane-like Cu4(μ3-I)4 cluster units are linked by the dithioether ligands. The crystallographically characterized one-dimensional (1D) compound [{Cu(μ2-Br)2Cu}{μ-PhS(CH2)3SPh}2]n (3) is obtained using CuBr. The outcome of the reaction of PhS(CH2)5SPh with CuI also depends of the metal-to-ligand ratio employed. Mixing CuI and the dithioether in a 2:1 ratio results in formation of [Cu4I4{μ-PhS(CH2)5Ph}2]n (4) in which cubane-like Cu4(μ3-I)4 clusters are linked by the bridging dithioether ligand giving ri...

Construction of (CuX)2n Cluster-Containing (X = Br, I; n = 1, 2) Coordination Polymers Assembled by Dithioethers ArS(CH2)mSAr (Ar = Ph, p-Tol; m = 3, 5): Effect of the Spacer Length, Aryl Group, and Metal-to-Ligand Ratio on the Dimensionality, Cluster Nuclearity, and the Luminescence Properties of the Metal–Organic Frameworks

The combination of the copper(i)-iodide entity with organic ligands gives rise to a large variety of CuII polynuclear structures in the form of molecular complexes or extended structures. An appropriate selection of these components allows the preparation of materials showing interesting physicochemical properties and potential applications, mainly focused on organic light-emitting diodes and optical sensors. The most prominent physical feature of these materials is their emission, which can be modulated using the chemical structure and composition. This review article collates the advances in this research field, rationalizing the information into two main blocks as a function of the dimensionality of the structures: molecular complexes and extended networks. We describe the most typical ways of preparation, structures, and properties, with particular attention to the processability of the material as a fundamental aspect of the integration of the materials into real devices. Therefore, we aim to integrate the basic elements of the coordination chemistry of CuII clusters from the materials science perspective to envision this promising research field's potential technological future.

Copper(i)-iodide cluster structures as functional and processable platform materials.

Measurement and correlation of solubility of ciclesonide in seven pure organic solvents

Varying the frameworks of coordination polymers with (CuI)4 cubane cluster by altering terminal groups of thioether ligands

For the purpose of enhancing the solubility and humidity stability of pymetrozine (PMZ), a highly active but nonbiocidal pesticide, new multicomponent crystals were developed based on the connotati...

New Salts and Cocrystals of Pymetrozine with Improvements on Solubility and Humidity Stability: Experimental and Theoretical Study

A series of boron-dipyrromethene dyes (BODIPYs) 4a-g with different thienyl moieties at 2,3,5,6-positions of the BODIPY core were synthesized by the Stille cross-coupling reaction. The new compounds were characterized by 1H NMR, 13C NMR, HRMS, and IR spectroscopy. The single crystal structure of compound 4e was obtained by X-ray crystallography. The optical and electrochemical properties of these dyes were studied by UV/Vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry. The DFT calculation of the frontier molecular orbitals of these dyes corroborates the observed effects of peripheral substituents on the optical and redox properties. These results reveal a good tunability of the optical and electronic properties of these BODIPYs by varying the peripheral groups at the α-positions of thienyl moieties, which leads to the absorption and emission reaching the NIR region.

Lina Zhou

Papers

Measurement and correlation of solubility of ciclesonide in seven pure organic solvents

Varying the frameworks of coordination polymers with (CuI)4 cubane cluster by altering terminal groups of thioether ligands

New Salts and Cocrystals of Pymetrozine with Improvements on Solubility and Humidity Stability: Experimental and Theoretical Study

Tetrathienyl-functionalized red- and NIR-absorbing BODIPY dyes appending various peripheral substituents.

Influence of Crystal Growth Conditions on Formation of Macroscopic Inclusions inside Thiourea Crystals