Structure, Spectroscopic Characterization and Application of Crystals

A new Cu(II) complex, [CuL₁L₂(CH₃COO)₂(H₂O)]·H₂O, was synthesized by the reaction of Cu(CH₃COO)₂·H₂O, 6-phenylpyridine-2-carboxylic acid (HL₁), and 4-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]pyridine (L₂) in ethanol-water (v:v = 1:1) solution. The Cu(II) complex was characterized using elemental analysis, IR, UV-vis, TG–DTA, and single-crystal X-ray analysis. The fluorescence properties of the copper complex were also evaluated. The structural analysis results show that the Cu(II) complex crystallizes in the triclinic system with space group P-1. The Cu(II) ion in the complex is five-coordinated with one O atom (O2) and one N atom (N1) from one 6-phenylpyridine-2-carboxylate ligand (L₁), one N atom (N2) from 4-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]pyridine ligand (L₂), one O atom (O4) from acetate, and one O atom (O5) from a coordinated water molecule, and it adopts a distorted trigonal bipyramidal geometry. Cu(II) complex molecules form a two-dimensional layer structure through intramolecular and intermolecular O-H^…O hydrogen bonding. The two-dimensional layer structures further form a three-dimensional network structure by π-π stacking interactions of aromatic rings. The analysis of the Hirschfeld surface of the Cu(II) complex shows that the H^…H contacts made the most significant contribution (46.6%) to the Hirschfeld surface, followed by O^…H/H^…O, N^…H/H^…N and C^…H/H^…C contacts with contributions of 14.2%, 13.8%, and 10.2%, respectively. In addition, the photocatalytic CO₂ reduction using Cu(II) complex as a catalyst is investigated under UV-vis light irradiation. The findings reveal that the main product is CO, with a yield of 10.34 μmol/g and a selectivity of 89.4% after three hours. Full article

A new bis-Schiff base (L) Ca(II) complex, CaL, was synthesized by the reaction of calcium perchlorate tetrahydrate, 1,3-diamino-2-hydroxypropane, and 2-formyl phenoxyacetic acid in an ethanol–water (v:v = 2:1) solution and characterized by IR, UV-vis, TG-DTA, and X-ray single crystal diffraction analysis. The structural analysis indicates that the Ca(II) complex crystallizes in the monoclinic system, space group P12₁/n1, and the Ca(II) ions are six-coordinated with four O atoms (O8, O9, O11, O12, or O1, O2, O4, O6) and two N atoms (N1, N2, or N3, N4) of one bis-Schiff base ligand. The Ca(II) complex forms a tetramer by intermolecular O-H^…O hydrogen bonds. The tetramer units further form a three-dimensional network structure by π–π stacking interactions of benzene rings. The Hirschfeld surface of the Ca(II) complex shows that the H^…H contacts represent the largest contribution (41.6%) to the Hirschfeld surface, followed by O^…H/H^…O and C^…H/H^…C contacts with contributions of 35.1% and 18.1%, respectively. To understand the electronic structure of the Ca(II) complex, the DFT calculations were carried out. The photocatalytic CO₂ reduction test of the Ca(II) complex exhibited a yield of 47.9 μmol/g (CO) and a CO selectivity of 99.3% after six hours. Full article

When it comes to crystal structure determination, computational approaches such as Crystal Structure Prediction (CSP) have gained more and more attention since they offer some insight on how atoms and molecules are packed in the solid state, starting from only very basic information without diffraction data. Furthermore, it is well known that the coupling of CSP with solid-state NMR (SSNMR) greatly enhances the performance and the accuracy of the predictive method, leading to the so-called CSP-NMR crystallography (CSP-NMRX). In this paper, we present the successful application of CSP-NMRX to determine the crystal structure of three structural isomers of pyridine dicarboxylic acid, namely quinolinic, dipicolinic and dinicotinic acids, which can be in a zwitterionic form, or not, in the solid state. In a first step, mono- and bidimensional SSNMR spectra, i.e., ¹H Magic-Angle Spinning (MAS), ¹³C and ¹⁵N Cross Polarisation Magic-Angle Spinning (CPMAS), ¹H Double Quantum (DQ) MAS, ¹H-¹³C HETeronuclear CORrelation (HETCOR), were used to determine the correct molecular structure (i.e., zwitterionic or not) and the local molecular arrangement; at the end, the RMSEs between experimental and computed ¹H and ¹³C chemical shifts allowed the selection of the correct predicted structure for each system. Interestingly, while quinolinic and dipicolinic acids are zwitterionic and non-zwitterionic, respectively, in the solid state, dinicotinic acid exhibits in its crystal structure a “zwitterionic-non-zwitterionic continuum state” in which the proton is shared between the carboxylic moiety and the pyridinic nitrogen. Very refined SSNMR experiments were carried out, i.e., ¹⁴N-¹H Phase-Modulated (PM) pulse and Rotational-Echo Saturation-Pulse Double-Resonance (RESPDOR), to provide an accurate N–H distance value confirming the hybrid nature of the molecule. The CSP-NMRX method showed a remarkable match between the selected structures and the experimental ones. The correct molecular input provided by SSNMR reduced the number of CSP calculations to be performed, leading to different predicted structures, while RMSEs provided an independent parameter with respect to the computed energy for the selection of the best candidate. Full article

Tin selenide (SnSe) holds great potential for abundant future applications, due to its exceptional properties and distinctive layered structure, which can be modified using a variety of techniques. One of the many tuning techniques is pressure manipulating using the diamond anvil cell (DAC), which is a very efficient in situ and reversible approach for modulating the structure and physical properties of SnSe. We briefly summarize the advantages and challenges of experimental study using DAC in this review, then introduce the recent progress and achievements of the pressure-induced structure and performance of SnSe, especially including the influence of pressure on its crystal structure and optical, electronic, and thermoelectric properties. The overall goal of the review is to better understand the mechanics underlying pressure-induced phase transitions and to offer suggestions for properly designing a structural pattern to achieve or enhanced novel properties. Full article