Physical and Chemical Interaction of Homoconjugated Dienes with Tetracyanoethylene

EDA-complexes of bicyclo[2,2,n]alkadienes (n = 1, 2, 3, 4) ( 1 (n)-series), 1,4-cyclohexadiene ( 2 ) and various other cyclic monoenes, dienes and trienes as donors and tetracyanoethylene (TCNE) as acceptor were investigated. Spectroscopic and thermodynamic constants of the complexes were determined and correlated with the ionisation potentials (I^D) of the hydrocarbon donors obtained from PE. spectroscopy. The nature of the dominant energy contributions to the ground state and the two lowest CT-states of these weak complexes is discussed and structural conclusions are drawn. The role of the complexes in the addition reaction of the hydrocarbon components and TCNE is discussed. The homo Diels-Alder addition product of 1 (2) and TCNE, 9,9,10,10-tetracyanoquadricyclo[2,2,2,0^2,6,2^3,5]decane, and the ‘ene’-addition product of 2 and TCNE, 5-[1′,1′,2′,2′-tetracyanoethyl]-1,3-cyclohexadiene were prepared and characterized. Preliminary results for the mechanistic scheme governing the dehydrogenation of 2 by TCNE are reported.     

Ab initio study of exchange coupling for the consistent understanding of the magnetic ordering at room temperature in V[TCNE] x

We report quantum chemical calculations providing the exchange coupling constants of the V[TCNE]₂ model system, describing the amorphous room temperature molecular magnet V[TCNE] _x (TCNE = tetracyanoethylene, x ~ 2). The geometry is optimized for the ideal lattice using density functional theory (DFT) calculations with periodic boundary conditions. Broken-symmetry DFT calculations indicate antiparallel spin alignment resulting in ferrimagnetic ordering, but heavily overestimate the value of the exchange coupling. Better estimates of the exchange coupling parameters between the V(II) ion and the [TCNE]^? anionic radical are obtained by means of multiconfigurational calculations performed on smaller molecular models cut from the optimized crystal lattice. Complete active space self-consistent field and multireference second-order perturbation theory calculations provide the sign and the strength of the nearest-neighbor as well as next-nearest-neighbor interactions along all three crystallographic directions. We are able to explain also intuitively the mechanism for antiferromagnetic spin coupling in terms of the superexchange pathways, discussing the role of the main four types of contributions to superexchange. Moreover, we clarify the influence of the transition metal ion on the strength of the exchange interaction and on the critical temperature for long-range ferrimagnetic ordering.     

Anomalous cluster glass behavior in a quasi-one-dimensional organic-based magnet

The spin glass transition of the quasi-one-dimensional (1D) organic-based magnet [MnTPP]⁺[TCNE]⁻ 2(1,3-C₆H₄Cl₂) (TPP is tetraphenylporphyrin dianion, TCNE is tetracyanoethylene) is explored using both a.c. and d.c. measurements. The a.c. susceptibility shows a strong frequency dependent peak consistent with a clustered spin glass state. Application of a d.c. magnetic field suppresses the peak in the a.c. susceptibility. Magnetic relaxation data can be fit to a stretched exponential, with the results reflecting a spin glass transition near 4 K. The spin cluster dimension and the effective dimension of the system are calculated within a fractal cluster model of spin glasses with values for the spin cluster dimension ranging from ∼0.8 to over 1.5 as the glass transition is approached.     

New Charge Transfer Complexes of K+-Channel-Blocker Drug (Amifampridine; AMFP) for Sensitive Detection; Solution Investigations and DFT Studies

UV–Vis spectroscopy was used to investigate two new charge transfer (CT) complexes formed between the K⁺-channel-blocker amifampridine (AMFP) drug and the two π-acceptors 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetracyanoethylene (TCNE) in different solvents. The molecular composition of the new CT complexes was estimated using the continuous variations method and found to be 1:1 for both complexes. The formed CT complexes’ electronic spectra data were further employed for calculating the formation constants (K_CT), molar extinction coefficients (ε_CT), and physical parameters at various temperatures, and the results demonstrated the high stability of both complexes. In addition, sensitive spectrophotometric methods for quantifying AMFP in its pure form were proposed and statistically validated. Furthermore, DFT calculations were used to predict the molecular structures of AMFP–DDQ and AMFP–TCNE complexes in CHCl₃. TD-DFT calculations were also used to predict the electronic spectra of both complexes. A CT-based transition band (exp. 399 and 417 nm) for the AMFP–TCNE complex was calculated at 411.5 nm (f = 0.105, HOMO-1 → LUMO). The two absorption bands at 459 nm (calc. 426.9 nm, f = 0.054) and 584 nm (calc. 628.1 nm, f = 0.111) of the AMFP–DDQ complex were theoretically assigned to HOMO-1 → LUMO and HOMO → LUMO excitations, respectively.     

Unusually long, multicenter, cation(δ+)···anion(δ-) bonding observed for several polymorphs of [TTF][TCNE

The α, β, and δ polymorphs of [TTF][TCNE] (TTF=tetrathiafulvalene; TCNE=tetracyanoethylene) exhibit a new type of long, multicenter bonding between the [TTF]^δ+ and [TCNE]^δ? moieties, demonstrating the existence of long, hetero‐multicenter bonding with a cationic^δ+???anionic^δ? zwitterionic‐like structure. These diamagnetic π‐[TTF]^δ+[TCNE]^δ? heterodimers exhibit a transfer of about 0.5 e^? from the TTF to the TCNE fragments, as observed from experimental studies, in accord with theoretical predictions, that is, [TTF^δ+???TCNE^δ?] (δ?0.5). They have several interfragment distances <3.4 Å, and a computed interaction energy of ?21.2 kcal mol^?1, which is typical of long, multicenter bonds. The lower stability of [TTF]^δ+[TCNE]^δ? with respect to typical ionic bonds is due, in part, to the partial electron transfer that reduces the electrostatic bonding component. This reduced electrostatic interaction, and the large interfragment dispersion stabilize the long, heterocationic/anionic multicenter interaction, which in [TTF^δ+???TCNE^δ?] always involves two electrons, but have ten, eight, and eight bond critical points (bcps) involving C? C, N? S, and sometimes C? S and C? N components for the α, β, and δ polymorphs, respectively. In contrast, γ‐[TTF][TCNE] possesses [TTF]₂²⁺ and [TCNE]₂^2? dimers, each with long, homo‐multicenter 2e^?/12c (c=center, 2 C+4 S) [TTF]₂²⁺ cationic⁺???cationic⁺ bonds, as well as long, homo‐multicenter 2e^?/4c [TCNE]₂^2? anionic^????anionic^? bonding. The MO diagrams for the α, β, and δ polymorphs have all of the features found for conventional covalent C? C bonds, and for all of the previously studied multicenter long bonds, for example, π‐[TTF]₂²⁺ and π‐[TCNE]₂^2?. The HOMOs for α‐, β‐, and δ‐[TTF][TCNE] have 2c C? S and 3c C? C? C orbital‐overlap contributions between the [TTF]^δ+? and [TCNE]^δ? moieties; these are the shortest intra [TTF???TCNE] separations. Thus, from an orbital‐overlap perspective, the bonding has 2c and 3c components residing over one S and four C atoms.     

Solid-State 13C NMR Evidence for Long Multicenter Intradimer Bonding in Zwitterion-like Structures

The principal values of the ¹³C chemical shift tensor for the β and δ polymorphs of π-[TTF⋅⋅⋅TCNE] (TTF=tetrathiafulvalene; TCNE=tetracyanoethylene) have been analyzed to understand the abnormally long intra-dimer bonding of singlet π-[TTF^δ+⋅⋅⋅TCNE^δ−]. These structures possess 12 intradimer contacts <3.40 Å, with the shortest intra π-[TTF⋅⋅⋅TCNE] separations involving 2-center (2c) C−S and 3c C−C−C orbital overlap contributions between the [TTF]^δ+ and [TCNE]^δ−. This solid-state NMR study compares the [TTF⋅⋅⋅TCNE] ¹³C tensor data against previously reported π-[TTF]₂²⁺ and π-[TCNE]₂²⁻ homo-dimers to determine how the tensor principal values change as a function of electronic structure for both TTF and TCNE moieties. In the β and δ phases of [TTF⋅⋅⋅TCNE], the TCNE ethylenic ¹³C shift tensors predict TCNE oxidation states of −0.46 and −0.73, respectively. The TTF sites are less similar to benchmark ¹³C data with the β-phase differing primarily in the ethylenic π-electrons. The δ form differs significantly from the homo-dimer data at all principal values at both the ethylenic and CH sites, indicating changes to both the π-electrons and σ-bonds. In both hetero-dimer phases, the NMR changes supports long bond formation at nitrile and CH sites not observed in homo-dimers.     

A New Conformation With an Extraordinarily Long, 3.04 Å Two‐Electron,Six‐Center Bond Observed for the π‐[TCNE]22− Dimer in [NMe4]2[TCNE]2 (TCNE=Tetracyanoethylene)

[NMe₄]₂[TCNE]₂ (TCNE=tetracyanoethenide) formed from the reaction of TCNE and (NMe₄)CN in MeCN has ν_CN IR absorptions at 2195, 2191, 2172, and 2156 cm^?1 and a ν_CC absorption at 1383 cm^?1 that are characteristic of reduced TCNE. The TCNEs have an average central C?C distance of 1.423 Å that is also characteristic of reduced TCNE. The reduced TCNE forms a previously unknown non‐eclipsed, centrosymmetric π‐[TCNE]₂^2? dimer with nominal C₂ symmetry, 12 sub van der Waals interatomic contacts <3.3 Å, a central intradimer separation of 3.039(3) Å, and comparable intradimer C???N distances of 3.050(3) and 2.984(3) Å. The two pairs of central C???C atoms form a ?C?C???C?C of 112.6° that is substantially greater than the 0° observed for the eclipsed D_2h π‐[TCNE]₂^2? dimer possessing a two‐electron, four‐center (2e^?/4c) bond with two C???C components from a molecular orbital (MO) analysis. A MO study combining CAS(2,2)/MRMP2/cc‐pVTZ and atoms‐in‐molecules (AIM) calculations indicates that the non‐eclipsed, C₂ π‐[TCNE]₂^2? dimer exhibits a new type of a long, intradimer bond involving one strong C???C and two weak C???N components, that is, a 2e^?/6c bond. The C₂ π‐[TCNE]₂^2? conformer has a singlet, diamagnetic ground state with a thermally populated triplet excited state with J/k_B=1000 K (700 cm^?1; 86.8 meV; 2.00 kcal mol^?1; H=?2 JS_a?S_b); at the CAS(2,2)/MBMP2 level the triplet is computed to be 9.0 kcal mol^?1 higher in energy than the closed‐shell singlet ground state. The results from CAS(2,2)/NEVPT2/cc‐pVTZ calculations indicate that the C₂ and D_2h conformers have two different local metastable minima with the C₂ conformer being 1.3 kcal mol^?1 less stable. The different natures of the C₂ and D_2h conformers are also noted from the results of valence bond (VB) qualitative diagram that shows a 10e^?/6c bond with one C???C and two C???N bonding components for the C₂ conformer as compared to the 6e^?/4c bond for the D_2h conformer with two C???C bonding components.     

Synthesis and characterization of electrically conducting polyaniline–TCNE complexes

Polyaniline–tetracyanoethylene (TCNE) complexes can be synthesized either from emeraldine base or emeraldine hydrochloride by a relatively simple method. The complexes demonstrate greater stability than the emeraldine hydrochloride at elevated temperatures and under high current densities. The electrical conductivity of the complexes synthesized from emeraldine base can be varied from < 10^?6 to 0.2 S/cm by varying the amount of TCNE incorporated. The complexes synthesized from emeraldine hydrochloride are slightly more conductive than the starting emeraldine hydrochloride. In both types of complexes, it appears that electron transfer between the polyaniline and TCNE has occurred resulting in the formation of some positively charged polyaniline nitrogen and TCNE anions.     

Organic and Organometallic Molecular Magnetic Materials—Designer Magnets

Magnets composed of molecular species or polymers and prepared by relatively low-temperature organic synthetic methodologies are a focus of contemporary materials science research. The anticipated properties of such molecular-species-based magnetic materials, particularly in combination with other properties associated with molecules and polymers, may enable their use in future generations of electronic, magnetic, and/or photonic/photronic devices ranging from information storage and magnetic imaging to static and low-frequency magnetic shielding. A tutorial of typical magnetic behavior of molecular materials is presented. The three distinct models (intramolecular spin coupling through orthogonal orbitals in the same spatial region within a molecule/ion, intermolecular spin coupling through pairwise “configuration interaction” between spin-containing moieties, and dipole—dipole, through-space interactions) which enable the design of new molecular-based magnetic materials are discussed. To achieve the required spin couplings for bulk ferro- or ferrimagnetic behavior it is crucial to prepare materials with the necessary primary, secondary, and tertiary structures akin to proteins. Selected results from the worldwide effort aimed at preparing molecular-based magnetic materials by these mechanisms are described. Some organometallic solids comprised of linear chains of alternating metallocenium donors (D) and cyanocarbon acceptors (A) that is, …?D^?+ A^?? D^?+ A^??…?, exhibit cooperative magnetic phenomena. Bulk ferromagnetic behavior was first observed below the critical (Curie) temperature T_c of 4.8 K for [Fe^III(C₅Me₅)₂]^?+ [TCNE]^?? (Me = methyl; TCNE = tetracyanoethylene). Replacement of Fe^III with Mn^III leads to a ferromagnet with a T_c of 8.8 K in agreement with mean-field models developed for this class of materials. Replacement with Cr^III, however, leads to a ferromagnet with a T_c lowered to 3.65 K which is at variance with this model. Extension to the reaction of a vanadium(o) complex with TCNE leads to the isolation of a magnet with a T_c ≈ 400 K, which exceeds the thermal decomposition temperature of the material. This demonstrates that a magnetic material with a T_c substantially above room temperature is achievable in a molecule/organic/polymeric material. Finally, a new class of one-dimensional ferrimagnetic materials based on metalloporphins is discussed.     

DFT investigation for 1:2 complexes of bis(hexafluoroacetylacetonato)copper(II) coordinated with 4-(N-tert-butyl-N-oxyamino)pyridine

With the aim to explore the nature of interaction between organic radicals and paramagnetic ion, unrestricted density functional theory (UDFT) and restricted open shell DFT (RO-DFT) calculations using 6-31G(d) and LANL2DZ basis sets have been performed on the 1:2 complexes of bis(hexafluoroacetylacetonato)copper coordinated with 4-(N-tert-butyl-N-oxyamino)pyridine, complex 1. Structural data revealed by X-ray crystal analysis are used. It is found that the calculated results depend on the selected functionals, model orientation, basis set form and symmetry constraint. The proper chemical models for investigated system are RO-B3LYP, RO-BLYP, RO-PBE, and RO-PBE0.     

Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations

Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]₂^2? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]₂^2? dimers form dissociated ion pairs with the NBu₄⁺ counterions, and their first solvation shell comprises approximately 20 CH₂Cl₂ molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE ^{. ?} in solution at 175 K is ?5.5 kcal mol^?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process.     

Ab initio MO Calculations of benzene + TCNE and naphthalene + TCNE complexes with STO-3G π-split basis set

Ab initio SCF MO calculations have been carried out on benzene + TCNE (tetracyanoethylene) and naphthalene + TCNE complexes with the STO -3G, STO -3G π-split (STO -3G for π orbitals and a split basis for π orbitals), and 4–31G basis sets. The interaction energy, gross charges, dipole moment, and the electron density in the middle plane of the complexes have also been evaluated. The STO -3G π-split basis set is appropriate for the calculation of large π–π stacking complexes from two points of view, production of reliable results and ease of computations. The approximation scheme based on the semiorthogonalized orgitals is revealed to be very efficient to save CPU time and storage in such calculations. The stable conformation and the charge-transfer interaction of the two complexes are discussed on the basis of the calculated quantities.     

DFT study of structure–properties correlations in [MnTPP][TCNE] quasi-one-dimensional molecular magnets

We report the first band structure calculations of the quasi-one-dimensional [MnTPP][TCNE] compounds (TPP = meso-tetraphenylporphyrinato, TCNE = tetracyanoethylene), based on Density Functional Theory (DFT) methods, in order to interpret the magnetic ordering in these prototypic systems. We compare and contrast the results of broken-symmetry DFT calculations for extended systems, with periodic boundary conditions, and for finite systems, magnetic dimers modeling the actual molecular magnets. By varying systematically the main angles, we are able to determine the geometry dependence of the exchange interaction. Structure–properties correlations in these charge-transfer salts reveal the determinant role of the Mn-(N≡C)_TCNE bond angle on the strength of the ferrimagnetic coupling between the S ₁ = 2 spin located on the Mn^III-porphyrin donor and the S ₂ = 1/2 spin positioned on the cyanocarbon acceptor. When the Mn-(N≡C)_TCNE angle is decreased, the intrachain magnetic coupling strengthens, correlated with the increase in the d_z² - p* d_{{z^{2} }} - \pi * orbital overlap. The exchange coupling constants resulting from DFT calculations of extended systems, with periodic boundary conditions, were found to be consistent with those obtained for the dimers, but systematically smaller. The exchange constants vary strongly with the functional used, hybrid functionals such as B3LYP leading to results that better correlate with the experimental mean-field critical temperatures. The coupling constant varies significantly with the type of broken-symmetry approach, depending on the overlap between magnetic orbitals, but weakly on the basis set once polarization effects are included. The electronic structure calculations for the extended systems provide a density of states consistent with the energy spectrum of the corresponding dimer, allowing for an intuitive explanation of the intrachain ferrimagnetic ordering.     

Evidence for the dimer-of-(mixed-valent dimers) configuration in tetranuclear {(μ4-TCNX)[Ru(NH3)5]4}8+, TCNX?=?TCNE and TCNQ, from DFT calculations

Abstract  

DFT calculations of the complex ions {(μ₄-TCNX)[Ru(NH₃)₅]₄}⁸⁺, TCNX = tetracyanoethene (TCNE) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ), yield triplet state energy minimum structures with nonplanar bridging ligands. The calculated C–C bond distances and twist angles confirm considerable metal-to-ligand electron transfer from the metal centers to the TCNE and TCNQ bridges in the lowest triplet and singlet states. The resulting situation, involving a weak interaction between two strongly coupled malonodinitrilato-bridged Ru^2.5Ru^2.5 entities (Class III), agrees with experimental results; the near-orthogonality found for the ground states of the molecular ions explains the observed magnetic exchange coupling between two S = 1/2 sites, the 1,258 cm⁻¹ absorption in the IR spectrum of the TCNE complex, and the reversible two-electron oxidation. The nitrile stretching frequency shifts were reasonably reproduced by the calculations. A density-of-states representation for the TCNQ complex shows a rather different electronic structure in comparison to that for the formally related {(μ₄-TCNQ)[Re(CO)₃(bpy)]₄}⁴⁺, in particular a different frontier orbital situation. In contrast to the (TCNQ⁰)(Re^I)₄ situation, the tetraruthenium species with an approximate (TCNX²⁻)(Ru^2.5)₄ formulation represent unconventional mixed-valent tetranuclear compounds; in other words, weakly coupled pairs of strongly coupled dinuclear moieties. EPR spectroscopy at the W band frequency (95 GHz) of the TCNE compound confirms that the reduction of the complex leads to the oxidation of TCNE²⁻ to yield a (TCNE^•−)(Ru^II)₄ species.     

Single-electron transfer upon formation of 2,2,3,3-tetracyano-1-phenyl-7,8-dithiabicyclo[3.2.1]octane from allyl dithiobenzoate and tetracyanoethylene. Electrochemical investigations

Studies by the method of cyclic potential scanning from 0.2 to 1.9 V provided electroanalytical evidence that the reaction of allyl dithiobenzoate with tetracyanoethylene (TCNE) in MeCN proceeds as the reaction of the TCNE^.− radical anion with the PhSSAll^.+ radical cation to form phenyl-substituted 2,2,3,3-tetracyano-7,8-dithiabicyclo[3.2.1]octane. When current is not applied, the reaction does not proceed at 20°C for 3 days. However, this reaction in boiling MeCN occurs without electrochemical activation and, apparently, involves intermediate formation of the above radical ions. It was established by semiempirical PM3 calculations that allyl dithiobenzoate and TCNE form a stable charge-transfer complex that precedes chemical electron transfer. Dedicated to the memory of Professor Viktor Nikolaevich Drozd. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 78–81, January, 1999.     

Do Antarafacial Cycloadditions Occur? Cycloaddition of Heptafulvalene with Tetracyanoethylene

The cycloaddition of heptafulvalene ( 1 ) with tetracyanoethylene (TCNE) was previously described as an example of an antarafacial cycloaddition, a [π¹⁴_a+π²_s] process that afforded only the trans cycloadduct by virtue of the edge-to-face approach of TCNE, facilitated by the S shape of 1 . The reaction has been investigated in depth and found not to be a concerted antarafacial process. At low temperature, the reaction is observed to give a mixture of cis and trans cycloadducts as well as a [4+2] cycloadduct. The mixture of products is converted to the trans cycloadduct by equilibration upon warming to room temperature. Studies with diethyl 2,3-dicyanofumarate and -maleate confirmed the formation of cis cycloadducts. DFT studies at the M06-2X/6-311+G(2d,p) SCRF=acetone level of theory show that the originally proposed edge-to-face approach of TCNE to 1 is highly disfavored, whereas a stepwise mechanism involving the addition of TCNE at C2 to form a zwitterion followed by collapse at either C2′ or C7′ is energetically accessible. The Diels-Alder adduct is also formed in a stepwise reaction by competitive addition of TCNE at C4 of 1 . These studies suggest that edge-to-face interactions are prohibitive in even the most favorable cases.     

Electron transfer reactions of (C5R5)2(CO)2Ti (R=H or Me) with TCNE or TCNQ: Spectroelectrochemical assignment of metal and ligand oxidation states in [(C5Me5)2(CO)Ti(TCNX)]

The TCNX ligands TCNE (tetracyanoethene) and TCNQ (7,7,8,8-tetracyano-p-quinodimethane) react instantaneously with (C₅R₅)₂(CO)₂Ti, R=H or Me, to yield highly air-sensitive mononuclear complexes (C₅R₅)₂(CO)Ti(TCNX) of which the soluble species (R=Me) were characterized also in the oxidized and reduced forms through cyclic voltammetry, EPR, IR and UV-vis spectroelectrochemistry. While oxidation at rather low potentials yields labile carbonyltitanium(IV) species of the TCNX⁻ ligands, the reduction occurs stepwise at unusually negative potentials, first on the ligand (to yield coordinated TCNX²⁻) and then on the metal (to form Ti^II). For the neutral complexes (C₅R₅)₂(CO)Ti^2+q(TCNX^−q) the results support a rather large amount of charge transfer 1<q<2 from the metal to the acceptors TCNX. Evidence for the previously formulated {(μ-TCNE²⁻)[(C₅H₅)₂Ti^IV(CO)]₂}(TCNE²⁻) could not be found. The complexes (C₅R₅)₂(CO)Ti(TCNE) are compared with related compounds (C₅R₅)₂BrV(TCNE), (C₆R₆)(CO)₂Cr(TCNE) and (C₅R₅)(CO)₂Mn(TCNE).     

Tetracyanoethylene substituted triphenylamine analogues

A set of tetracyanoethylene (TCNE) substituted triphenylamine analogues (4–6) exhibiting strong intramolecular charge transfer (ICT) were designed and synthesized by the [2+2] cycloaddition–retroelectrocyclization reaction of 3 (tris-(4-phenylethynyl-phenyl)-amine) with TCNE. The reaction was found to be temperature dependent. The blue shift in the π → π¹ transition and intramolecular charge transfer (ICT) in amines 4–6 were found to be directly proportional to the number of TCNE units. The computational study shows good agreement with the experimental results and reveals that as the number of TCNE units in amine increases, HOMO–LUMO gap increases.     

Spectroscopic studies,Density Functional Theory calculations,and non-linear optical properties of binuclear Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) complexes of OONN Schiff base ligand

The binuclear complexes of Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) with 2-[3-(benzylideneamino)-2-(benzylidenehydrazono)-4-oxothiazolidin-5-yl] acetic acid ligand (HL) were prepared and their stoichiometry was determined by elemental analysis. The stereochemistry of the studied binuclear metal complexes was confirmed by analyzing their infrared spectra, ¹H NMR, and magnetic moment. Thermal decomposition studies of the binuclear complexes have been performed to demonstrate the status of water molecules present in these binuclear complexes and their general decomposition pattern. The equilibrium geometry of the ligand and its studied complexes were calculated using density function theory (DFT) calculations at the B3LYP/GENECP level of the theory. The results show that the ligand and its complexes are nonplanar structures as indicated from the values of the dihedral angles. Extent of distortion from regular geometry has been performed and discussed in terms of the values of the angles between the central metals and the coordinated sites. The E_HOMO and E_LUMO energies of the studied ligand and its complexes are used to calculate the global properties. The nonlinear optical parameters (NLO), anisotropy of the polarizibility (Δα), and the mean first-order hyperpolarizability (<β>) were calculated. The (<β>) values were compared with Urea as a reference molecule and the results of (<β>) values showed that the ligand and the studied complexes have good NLO behaviors.