Synthesis, Structural, and Intriguing Electronic Properties of Symmetrical Bis-Aryl-α,β-Unsaturated Ketone Derivatives

Abstract

Three symmetrical bis-aryl-α,β-unsaturated ketone derivatives, 2,6-di((E)-benzylidene)-cyclohexan-1-one (DBC), 2,6bis((E)-4-chlorobenzylidene)cyclohexan-1-one (BCC), and (1E,1′E,4E,4′E)-5,5′-(1,4-phenylene)bis(2-methyl-1-phenylpenta-1,4-dien-3-one) (PBMP), have been prepared using the aldol condensation approach toward ketones having two enolizable sites. The structures of DBC, BCC, and PBMP have been resolved via spectrometric methods. Moreover, the crystal structure of PBMP is determined by the single-crystal X-ray diffraction (SC-XRD) technique, which revealed that the PBMP molecular assembly is stabilized by the intermolecular C−H•••O bonding and C− O•••π and weak T-shaped offset π•••π stacking interactions. The Hirshfeld surface analysis (HSA) of the PBMP crystal structure was performed as well, and the results were compared with the results of DBC and BCC. The density functional theory (DFT) study results revealed that the longer conjugated molecule of PBMP has smaller but still quite significant HOMO−LUMO gaps compared to the smaller molecules of BCC and DBC.The natural population analysis (NPA) and natural bonding orbital (NBO) analysis were performed. Accordingly, the hydrogen bonding and dipole−dipole interactions stabilize the crystal structures of these compounds. Additionally, the NBO analysis showed numerous high-energy stabilizing interactions for the PBMP compound due to the presence of numerous delocalized and relatively easily polarizable π-electrons, thus implying its significant thermodynamic stability. According to the global reactivity parameter (GRP) analysis, the compounds BCC and DBC are relatively stable in redox processes and have high thermodynamic stability and relatively lower reactivity in general. The molecular electrostatic potential (MEP) analysis results imply potential formation of the intermolecular hydrogen bonding and dispersion interactions, which stabilizes the crystal structures of these compounds.

Stabilization of Palladium-Nanoparticle-Decorated Postsynthesis-Modified Zr-UiO-66 MOF as a Reusable Heterogeneous Catalyst in C–C Coupling Reaction

“…The growth of a C–C bond is a consequence of a cross-coupling reaction, defined as the substitution of a heteroatom nucleophile for an alkyl, aryl, or vinyl halide . Multiple aryl derivatives may be made in one go with high selectivity and without the need for an intermediate product isolation. − Also, cross-coupling reactions are considered as a protagonist, which is specifically utilized in the synthesis of diverse symmetric and asymmetric heteroaryl and biaryl patterns which are essential as vital building structures to provide natural products; pharmaceuticals including important hypertensive, fungicide, antimicrobial, antidiabetic, and analgesic pharmaceutical structures; the antibiotic vancomycin; and anticancer drugs. − …”

A Comprehensive Investigation into the Crystallology, Molecule, and Quantum Chemistry Properties of Two New Hydrous Long-Chain Dibasic Ammonium Salts CnH2n+8N2O6 (n = 35 and 37)

“…The ability of a pair of chemical species (X, Y) to form crystal packing interactions is determined by computing the enrichment ratio. The enrichment ratio is calculated by dividing the proportion of the actual contacts by the theoretical proportion of the random contacts [ 48 , 49 , 50 ]. For a particular crystal, some contacts are more favorable to forming crystal packing interactions than other contacts.…”

Synthesis, Characterization, Crystal Structures, and Supramolecular Assembly of Copper Complexes Derived from Nitroterephthalic Acid along with Hirshfeld Surface Analysis and Quantum Chemical Studies

“…The propensity of one pair is different from other pairs. The enrichment ratio provides the propensity by dividing the proportion of the actual contacts in the crystal by the theoretical proportion of the random contacts. − Tables S1 and S2 list the enrichment ratio of the pair of chemical moieties in Cu-NTA and Cu-DNTA , respectively. The contacts with an enrichment ratio greater than one have a higher propensity to generate crystal-packing interactions relative to other contacts.…”