On the Performance of Hybrid Functionals for Non-linear Optical Properties and Electronic Excitations in Chiral Molecular Crystals: The Case of Butterfly-Shaped Dicinnamalacetone.

Purely organic chiral molecular assemblies in the solid state hold great potential for non-linear optical applications. Herein, a newly synthesised molecular system is reported, namely, dicinnamalacetone, an otherwise planar molecule that crystallises in a disordered non-centrosymmetric form with four different conformations having an overall predominance of a particular helicity. A combined experimental and theoretical approach, including single-crystal X-ray diffraction, Kurtz-Perry and ab initio methods, is employed to characterise the system and benchmark the performance of hybrid functionals for the prediction of non-linear optical properties and electronic excitations.

Structure and NIR-luminescence of ytterbium(III) beta-diketonate complexes with 5-nitro-1,10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact.

Seven new tris(β-diketonear-nate)ytterbium(III) complexes with the general formula [Yb(β-diketonate)3(5NO2phen)] (where the β-diketone is either 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 2,4-hexanedione or 2,6-dimethyl-3,5-heptanedione, and 5NO2phen = 5-nitro-1,10-phenanthroline) were synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Single crystal X-ray structures have been determined for three fluorinated complexes and ground state geometries of the other four complexes have been predicted using the Sparkle/PM6 model. These experimental structures and those designed by semi-empirical models reveal octacoordination around the Yb(3+) ion.

Poly[piperazine-1,4-diium [μ(4)-chlorido-μ(3)-chlorido-tri-μ(2)-chlorido-chloridodicadmate(II)] monohydrate].

In the title compound, {(C(5)H(14)N(2))[Cd(2)Cl(6)]·H(2)O}(n), the asymmetric unit contains one piperazinediium cation, one [Cd(2)Cl(6)](2-) anion and a water mol-ecule. The coordination geometries of the two Cd(2+) cations are distorted octa-hedral. Adjacent Cd(II) atoms are inter-connected alternately by paired chloride bridges, generating polymeric chains parallel to [010].