A theoretical investigation of the fragment interaction and nonlinear optical and electronic properties of tris(β-diketonato)iron(III) complexes

被引:0
作者
Adeniyi, Adebayo A. [1 ,2 ]
Conradie, Jeanet [1 ]
机构
[1] Univ Free State, Dept Chem, POB 339, ZA-9300 Bloemfontein, South Africa
[2] Fed Univ Oye Ekiti, Dept Chem, Oye, Ekiti, Nigeria
基金
新加坡国家研究基金会;
关键词
mer and fac isomers; Hyperpolarisability; Nonlinear optical; Ligand-metal interaction; NEDA; Electrophilicity and nucleophilicity; FREQUENCY-DEPENDENT HYPERPOLARIZABILITIES; DENSITY-FUNCTIONAL THEORY; CHARGE DECOMPOSITION ANALYSIS; CONFORMATIONAL STABILITY; MOLECULAR-INTERACTIONS; SOLVENT-EXTRACTION; BASES PRINCIPLE; FUKUI FUNCTION; METAL-COMPLEX; SOFT ACIDS;
D O I
10.1007/s11224-019-01388-9
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This study presents the effects of substituent groups R-1 and R-2 of beta-diketonato ligands (R1COCHCOR2)(-) in [Fe(beta-diketonato)(3)] complexes, on the interaction energy between the ligand fragments and the central iron(III) atom, coupled with the nonlinear optical properties and electronic properties of the [Fe(beta-diketonato)(3)] molecules. The results show that a CF3 group on the ligand reduces the nucleophilicity of the Fe atom and favours stability of the mer isomer above the fac isomer, contrary to what is observed in other unsymmetrically substituted molecules without a CF3 substituent group. The reduction of the molecules results in the weakening of the Fe-O coordination bonds, but increasing strength of the C-O covalent bonds of the ligands. The molecules that have favourable experimental reduction potentials (more positive values) are characterised by lower ionisation potential of the reduced iron(II), lower inductive effect and a lower energy of the lowest occupied molecular orbital (LUMO) before reduction (iron(III)), but by higher chemical potential and higher LUMO energy level after reduction (iron(II)). The experimental reduction potentials are found to correlate significantly with the inter-fragment total energy of interaction (Delta E-tot) between the beta-diketonato ligands and the iron(III) atom (R-2 = 0.948), with a mean absolute deviation (MAD) of the predicted reduction potential of 0.073. Also, the contribution of electrical energy (EL) to the interaction energy (Delta E-tot) correlates significantly with the experimental reduction potential (R-2 = 0.951), resulting in an even better prediction of reduction potential (MAD = 0.067). It is observed that ring substituents (Ph, C4H3O, C4H3S), dipole moment and polarisability have a greater effect on the hyperpolarisability of the molecules, than merely the presence of a more withdrawing substituent, like CF3. Therefore, molecule [Fe(PhCOCHCOH)(3)] with a phenyl ring substituent is found to be the compound best suited for nonlinear optical (NLO) applications, extraordinarily higher than the other molecules of this study.
引用
收藏
页码:215 / 232
页数:18
相关论文
共 62 条
[1]   The stability, kinetics and inter-fragment electron communication of the tautomers of twelve selected β-diketone molecules: A computational study [J].
Adeniyi, Adebayo A. ;
Conradie, Jeanet .
JOURNAL OF MOLECULAR GRAPHICS & MODELLING, 2018, 85 :25-39
[2]   Intra-molecular electron communication, spectroscopic and conformational stability of the newly developed urethane modified polyetheramide coatings: Computational methods [J].
Adeniyi, Adebayo A. ;
Akintayo, Cecilia O. ;
Akintayo, Emmanuel T. ;
Conradie, Jeanet .
JOURNAL OF MOLECULAR GRAPHICS & MODELLING, 2017, 78 :1-13
[3]  
[Anonymous], 2018, CAMBRIDGE STRUCTURAL
[4]  
Arulmozhiraja S, 1997, MOL PHYS, V90, P55, DOI 10.1080/00268979709482586
[5]   Variational principles for describing chemical reactions: The Fukui function and chemical hardness revisited [J].
Ayers, PW ;
Parr, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (09) :2010-2018
[6]   A SIMPLE MEASURE OF ELECTRON LOCALIZATION IN ATOMIC AND MOLECULAR-SYSTEMS [J].
BECKE, AD ;
EDGECOMBE, KE .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (09) :5397-5403
[7]   A PERTURBATION METHOD FOR CALCULATING VIBRATIONAL DYNAMIC DIPOLE POLARIZABILITIES AND HYPERPOLARIZABILITIES [J].
BISHOP, DM ;
KIRTMAN, B .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (04) :2646-2658
[8]   Iron-catalyzed reactions in organic synthesis [J].
Bolm, C ;
Legros, J ;
Le Paih, J ;
Zani, L .
CHEMICAL REVIEWS, 2004, 104 (12) :6217-6254
[9]   An 'atoms in molecules' (AIM) analysis of the dihydrogen bond in organometallic compounds [J].
Calhorda, MJ ;
Lopes, PEM .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 609 (1-2) :53-59
[10]   Update 1 of: Electrophilicity Index [J].
Chattaraj, Pratim Kumar ;
Roy, Debesh Ranjan .
CHEMICAL REVIEWS, 2007, 107 (09) :PR46-PR74