Crystal structure, DFT-study and NLO properties of the novel copper(I) nitrate π,σ-coordination compound based on 1-allyl-3-norbornan-thiourea

• Published in: Polyhedron Vol. 211; pp. 115545 - 115551
• Main Authors: Slyvka, Yurii, Fedorchuk, Andrii A., Goreshnik, Evgeny, Pokhodylo, Nazariy, Jedryka, Jaroslaw, Ozga, Katarzyna, Mys'kiv, Marian
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 01.01.2022; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Copper(I) π-coordination compound; Crystal structure; Crystallography; DFT; N-allylthiourea; NLO; Physical Sciences; Science & Technology; NLO; Copper(I) π-coordination compound; DFT; N-allylthiourea; Crystal structure; LIGAND SYNTHESIS; CURRENT ELECTROCHEMICAL CRYSTALLIZATION; THIOUREA; UREASE INHIBITORS; DFT NLO; COMPLEXES BEARING; ALLYLTHIOUREA; SINGLE-CRYSTAL; Copper(I) pi-coordination compound; PI-COMPLEXES; DERIVATIVES; CHLORIDE
• ISSN: 0277-5387; 1873-3719
• DOI: 10.1016/j.poly.2021.115545

Novel [CuI(Anor)(CH3CN)](NO3) (1) π-complex with 1-allyl-3-norbornan-thiourea (Anor) was obtained by ac-electrochemical technique. Both organic compound (Anor) and complex 1 were structurally characterized. In both Anor and 1 crystal structures the organic part is disordered because of superposition of (2S)-exo and (2R)-exo enantiomers. The optimized geometry and some NLO parameters were found using DFT calculation. A high coherent laser stimulated effective second harmonic generation was established. [Display omitted] This work is directed toward the synthesis, structural characterization and NLO properties investigation of the novel copper(I) nitrate π,σ-coordination compound [Cu(Anor)(CH3CN)](NO3) (1) based on 1-allyl-3-norbornan-thiourea (Anor). In the crystal structure of both Anor and 1, the organic part is disordered because of the superposition of (2S)-exo and (2R)-exo enantiomers. The Anor ligand in 1 acts as a bridging ligand, connecting Cu(I) ions into the cationic coordination polymer {[Cu(Anor)(CH3CN)]+}n through η2-allyl group and the thiourea S atom. The H atoms of the –NH– groups in the Anor structure participate in NH···S hydrogen bonding and form an infinite hydrogen-bonded layer, while the same ligand groups in the organometallic chain of 1 are linked by bifurcated NH···O bonds to the two O atoms of the same NO3– anion. The second-order nonlinear optical properties for Anor and coordination compound 1 were studied at 1064 nm generated by a nanosecond pulsed Nd:YAG laser. The corresponding values of the average first-order NLO hyperpolarizabilities calculated by the DFT method and the B3LYP functional for the Anor ligand molecule and the cation fragment confirm the experimentally determined much higher second-harmonic generation efficiency for compound 1.