Crystal structure, DFT-study and NLO properties of the novel copper(I) nitrate π, σ-coordination compound based on 1-allyl-3-norbornan-thiourea. (1st January 2022)

• Record Type: Journal Article
• Authors: Slyvka, Yurii; Fedorchuk, Andrii A.; Goreshnik, Evgeny; Pokhodylo, Nazariy; Jedryka, Jaroslaw; Ozga, Katarzyna; Mys'kiv, Marian
• Is Part Of: Polyhedron. Volume 211(2022)
• Publication Date: 2022-01-01
• Subjects: Copper(I) π-coordination compound -- N-allylthiourea -- Crystal structure -- DFT -- NLO; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2021.115545
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Novel [Cu I ( Anor )(CH3 CN)](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. Abstract: 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 )(CH3 CN)](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 )(CH3 CN)] + }n through η 2 -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 .