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Synthesis, crystal structure, and DFT study of two new dinuclear copper(I) complexes bearing Ar-BIAN ligands functionalized with NO2 groups
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Advisor(s)
Abstract(s)
Two new bis(aryl-imino)-acenaphthene, Ar-BIAN (Ar = 2,4,6-trimethylphenyl = mes) ligands, bearing the NO2
group in the naphthalene moiety of the iminoacenaphthene at para- (5-NO2) and meta- (4-NO2) position, of formulations 1,2-bis(mes-imino)-5-nitroacenaphthene, 1, and 1,2-bis(mes-imino)-4-nitroacenaphthene, 2, were synthesized. Their respective dinuclear iodide bridged copper(I) complexes [Cu2(μ-I)2(mes-BIAN-5-NO2)2], 3 and [Cu2(μ-I)2(mes-BIAN-4-NO2)2], 4, were obtained in good yields by treatment with an equimolar amount
of CuI. All compounds were characterized by elemental analysis, single-crystal X-ray diffraction, 1H-NMR, 13C-NMR, FTIR, UV/Vis spectroscopy. DFT calculations helped to understand the different molecular structure observed in the crystals of 3 and 4 and the determining role of packing forces. TDDFT revealed that the
absorption bands in the visible were essentially MLCT (Metal to Ligand Charge Transfer), with some n→π* character (intra ligand). The shift to the red compared to the spectrum of the Cu(I) complex analogue without the NO2 group, [Cu2(μ-I)2](mes-BIAN)2], 6, could be explained by the stabilization of the ligand unoccupied π* orbitals in the presence of NO2.
Description
Acknowledgments : This work was supported by the Associate Laboratory for Green Chemistry- LAQV financed by national funds from FCT/MCTES (UIDB/50006/2020). M. J. C. and M. O. acknowledge the Fundação para a Ciência e a Tecnologia (FCT) for support (UIDB/04046/2020 and UIDP/04046/2020). The authors acknowledge LabRMN at FCT-UNL and Rede Nacional de RMN (RNRMN) for
access to the facilities. The NMR spectrometers are part of The National NMR Facility, supported by FCT (ROTEIRO/0031/2013 - PINFRA/22161/2016) (co-financed by FEDER through COMPETE 2020, POCI, and PORL and FCT through PIDDAC). Data Mass
Spectrometry obtained by the Laboratório de Análises/LAQV REQUIMTE - Chemistry department FCT University NOVA of Lisbon. The SCXR determinations were performed in house (equipment financed by national funds through project RECI/BBB-BEP/0124/2012 from FCT/MCTES). S. B. acknowledges project SmartBioR for financial support (CENTRO-01–0145-FEDER-000018, Integrated Programme SR&TD co-funded by Centro 2020 program, Portugal 2020, European Union, through the European Regional Development Fund). M. O. acknowledges PhD Grant SFRH/BD/120985/2016 financed by FCT.
Keywords
Copper(I) Functionalized Ar-BIAN Synthesis Density function calculations Crystal structure
Pedagogical Context
Citation
Outis, M, Rosa V, Laia CAT, Lima JC, Barroso S, Carvalho AL, Calhorda MJ, Avilés T. 2020. Synthesis, Crystal Structure, and DFT Study of Two New Dinuclear Copper(I) Complexes Bearing Ar-BIAN Ligands Functionalized with NO2 Groups. European Journal of Inorganic Chemistry. 2020:2900-2911., Number 30
Publisher
Wiley