Structures and enhanced third-order nonlinear optical performance of four complexes investigated by thin film <Emphasis Type="Italic">Z-</Emphasis>scan technique

Four transition metal complexes have been synthesized via hydrothermal reactions, namely, [Zn(1,3-BIB)(CH₃COO)₂]₂ 1, [Cu₂(1,4-BIB)₃(CO₃)₂](1,4-BIB)·10H₂O 2, {[Mn(H₂O)₂(1,2-BIB)₂]Cl₂}_n 3, and {[Mn(1,2-BIB)(1,4-NDC)]₂}_n 4, where 1,n-BIB = 1,n-bis(imidazol-l-yl-methyl)benzene, n = 2, 3, 4 and 1,4-NDC = naphthalene-1,4-dicarboxylic acid. Complex 1 presents a discrete ring-like structure. Complex 2 shows a ladder-like chain structure, while complex 3 has a joint-like chain structure. Complex 4 features a layer structure constructed from [Mn₂(N₄O₈)] clusters. The third-order nonlinear optical (NLO) properties of these complexes in thin films have been investigated by employing the Z-scan technique. Complexes 1–3 exhibit strong third-order NLO reverse-saturable absorption, while 4 shows third-order NLO saturable absorption and a strong self-defocusing effect. The third-order NLO susceptibilities χ ⁽³⁾ of the four complexes were calculated as 2.74 × 10^?9, 12.24 × 10^?9, 42.78 × 10^?9 and 189.32 × 10^?9 esu, respectively. The electronic structures of the complexes were investigated by density functional theory, and the origins of their NLO properties are discussed.     

Theoretical study in gas phase of linear and nonlinear optical properties of the ortho-, meta- and para-nitrophenol isomers

The linear (α), and nonlinear (β, γ) optical NLO properties of ortho-, meta- and para-nitrophenol (ONP, MNP and PNP) isomers have been calculated in gas phase by using ab initio (HF, MP2 and MP4) and density functional theory (DFT) (B3LYP, CAM-B3LYP) methods, with the 6-31+G(d,p) and 6-311+G(3d,3p) standard and the Sadlej specialized basis sets. These properties were evaluated both at static and at dynamic regime within the finite field FF numerical techniques and the time-dependent-Hartree–Fock approach at 1,910 nm, respectively. Additional calculations were performed for the β static hyperpolarizability of these isomers in presence of p-dioxane solvent with the Onsager Model and the SCRF-PCM approach, using B3LYP/6-31+G(d,p) and MP2/6-31+G(d,p) levels of theory. Additionally, CCSD/6-31+G(d,p) calculations were performed for the α, β and γ properties of PNP isomer. The B3LYP and MP2 α _ave results of the nitrophenol isomers are comparable to the experimental α _ave reports; while the tendency for the β _v calculated values (β _v PNP > β _v MNP > β _v ONP), that can be explained in terms of the O _x atomic charge of the –NO₂ group, does not follow exactly the experimental ones. The B3LYP γ _ave results are in correspondence to the experimental measurements, the correlation of which is r ² = 0.99. The use of FF methodology in conjunction with the B3LYP and MP2 methods and the 6-31+G(d,p) basis set show to be appropriate approaches to predict qualitative optical properties of Push–Pull like organic molecules, provided are considered the solvent effects or frequency dependence. However, to have a clear picture of the NLO properties of an isolated molecule, higher order correlation effects combined with specialized basis sets, frequency and solvent effects should be employed. We have demonstrated that MP4/Sadlej level of theory is able to reproduce NLO properties that can be considered equivalent to those from more sophisticated approaches, such as CCSD together with extended basis sets.     

Influence of acceptor tethering on the performance of nonlinear optical properties for pyrene-based materials with A-π-D-π-D architecture

In this study, we designed a series of pyrene-based donor-π-donor-π-acceptor compounds (HPTC1-HPTC7) by structural tailoring the reference compound (HPTC) using acceptor units. Nonlinear optical (NLO) properties, frontier molecular orbitals (FMOs), natural bonding orbital (NBO), transition density matric (TDM) analysis, and absorption spectra of reference and proposed derivatives were calculated at M06/6-31G(d,p) functional. All the designed compounds have smaller energy bandgaps than the HPTC compound. Moreover, the designed compounds exhibited larger global softness values than the reference. The absorption maxima of HPTC2, HPTC3, and HPTC7 are blue shifted with respect to HPTC. NBO analysis revealed that prolonged hyper conjugative associations and strong interactions between the donor (π) and acceptor (π*) moieties play a crucial part in their stabilization. The FMO and NBO findings supported the NLO responses of entitled compounds, and consequently, the linear and nonlinear properties of designed derivatives elevate compared to the reference molecule. Promisingly, the NLO response for HPTC7 comprises of highest values of <α>, β_total and < γ > as 1.92 × 10^?22 esu, 1.95 × 10^?27 esu, and 4.69 × 10⁷ (a.u). This NLO behavior shows push–pull NLO chromophores for HPTC7 predicting its role in pursuing NLO materials for optoelectronic applications.     

Triethylammonium picrate: An above-room-temperature phase transition material to switch quadratic nonlinear optical properties

Quadratic nonlinear optical properties of the picrate-based molecular crystal have been switched using the order-disorder phase transition, which opens up a potential way to design stimuli-responsive materials.     

Thermochemistry of piperidine adducts of some bivalent transition metal bromides

The adducts [MBr₂(pipd) _n ] (where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), or Zn(II); pipd = piperidine; n = 1/2, 1, or 3/4) were synthesized and characterized by melting points, elemental analysis, thermal studies, and IR and electronic spectroscopy. From calorimetric studies in solution, the standard enthalpies of formation and several other thermochemical parameters of them were determined. The mean standard enthalpies of the metal–nitrogen bonds were calculated, as well as the enthalpies of the adduct formation in the gaseous phase. Using the values obtained for the enthalpies of reaction, the acidity order of the salts is obtained: FeBr₂ > MnBr₂ and CoBr₂ > NiBr₂. Comparing with pyridine adducts, the ligand piperidine is more basic than the ligand pyridine: pipd > py.     

Chemical and electrochemical behavior of metallic technetium in acidic media

The chemical and electrochemical properties of technetium metal were studied in 1–6 M HX and in 1 M NaX (pH 1 and 2.5), X = Cl, NO₃. The chemical dissolution rates of Tc metal were higher in HNO₃ than in HCl (i.e. 8.63 × 10^?5 mol cm^?2 h^?1 in 6 M HNO₃ versus 2.05 × 10^?9 mol cm^?2 h^?1 in 6 M HCl). The electrochemical dissolution rates in HNO₃ and HCl were similar and mainly depended on the electrochemical potential and the acid concentration. The optimum dissolution of Tc metal was obtained in 1 M HNO₃ at 1 V/AgAgCl (1.70 × 10^?3 mol cm^?2 h^?1). The dissolution potentials of Tc metal in nitric acid were in the range of 0.596–0.832 V/AgAgCl. Comparison of Tc behavior with Mo and Ru indicated that in HNO₃, the dissolution rate followed the order: Mo > Tc > Ru, and for dissolution potential the order: E _diss(Ru) > E _diss(Tc) > E _diss(Mo). The corrosion products of Tc metal were analyzed in HCl solution by UV–Visible spectroscopy and showed the presence of TcO₄ ^?. The surface of the electrode was characterized by microscopic techniques; it indicated that Tc metal preferentially corroded at the scratches formed during the polishing and no oxide layer was observed.     

Tailoring the donor moieties in TPA-based organic dyes for efficient photovoltaic,optical and nonlinear optical response properties

The current study reports tailoring the electronic donor structures of organic dyes to modify their optical and nonlinear optical (NLO) response properties. Five (5) tri-phenyl amine (TPA) based Donor-π-Acceptor (D-π-A) organic dyes with the codes ICAA1 , ICAA2 , ICAA3 , ICAA4 , and ICAA5 were designed and investigated for their optical and NLO properties using quantum chemical methods. Optical and NLO properties of these dyes were studied by CAM-B3LYP method and 6-311G* basis set. The focus has been on the impact of adding secondary donors and shifting their substitutions at ortho (o), meta (m) and para (p) positions. Among all designed compounds, ICAA4 showed the highest amplitude of average third-order NLO polarizability <γ>, which is calculated to be 1316 × 10⁻³⁶ esu. Time-dependent Density Functional Theory (TD-DFT) method was used to determine how a change in the position of the donor affected the excitation energy (E_g) and NLO response properties. The findings showed that changing the position of the secondary donor results in a red shift among absorption spectra as well as the increase in their NLO responses. Complete process of intramolecular charge transfer (ICT) has been investigated in terms of different optical parameters such as frontier molecular orbitals (FMOs), molecular electrostatic potentials (MEPs), transition density matrix (TDMs), density of states (DOS), electron density difference (EDD), and natural bond orbital (NBO) analysis. Our calculations for study of ICT process indicate that p-position of methoxy group performs better among all other positions and even it has better NLO response properties than the compound with three collective methoxy groups. The calculated V_oc values of all designed molecules range from 1.09 to 1.30, all of them are positive while their ΔG_inject is found to be in the range of −0.87 to −1.79 eV indicating their decent potential for photovoltaic applications. The studied optical, NLO and photovoltaic parameters illustrated that ICAA1 to ICAA5 are appropriate molecules not only for NLO applications but also for efficient photovoltaic purposes.     

Herinase: A Novel Bi-functional Fibrinolytic Protease from the Monkey Head Mushroom, Hericium erinaceum

Herinase, a new bi-functional fibrinolytic metalloprotease, was purified from a medicinal and edible mushroom Hericium erinaceum. The enzyme was monomeric with a molecular mass of 51 kDa. Analysis of fibrin zymography showed an active band with a similar molecular mass. The N-terminal sequence of herinase VPSSFRTTITDAQLRG was highly distinguished from known fibrinolytic enzymes. Moreover, the enzyme activity was strongly inhibited by EDTA and EGTA, indicating that herinase is a metalloprotease. Herinase exhibited high specificity for the substrate t-PA followed by plasmin. The K _m and V _max values for H-D-Ile-Pro-Arg-PNA were found to be 4.7 mg and 26.7 U/ml respectively. Similarly, fibrin plate assays revealed that it was able to degrade fibrin clot directly and also able to activate plasminogen. Herinase provoked a rapid degradation of fibrin and fibrinogen α chains and slower degradation of γ chains. It had no activity on the β chains of fibrin and fibrinogen. This result suggests that herinase could possibly contain higher amount of α-fibrinogenase. The activity of herinase was stimulated by metal ions such as Ca²⁺, Mg²⁺, and Mn²⁺, but inhibited by Cu²⁺, Fe²⁺, and Zn²⁺. Herinase exhibited maximum activity at 30 °C and pH 7.0. These results demonstrate that herinase could be a novel fibrinolytic enzyme.     

Effects of calcination and support on supported manganese catalysts for the catalytic oxidation of toluene as a model of VOCs

The conventional impregnation method was used to prepare 15 wt% Mn-supported catalysts, which were applied to the catalytic oxidation of volatile organic compounds (VOCs; toluene, benzene, and o-xylene). The effects of calcination temperatures in the range of 500–900 °C and supports (γ-Al₂O₃, SiO₂, and TiO₂) on the property and performance of 15 wt% Mn-supported catalysts were investigated. Their physicochemical characteristics were analyzed by the BET, XRD, NH₃–TPD, H₂–TPR, and XPS. The calcination temperature greatly affected the crystalline structure and O1s _D (defect oxides)/O1s _L (lattice oxides) area ratio of the 15 wt% Mn/γ-Al₂O₃ (15 Mn/Al) catalyst. The order of the O1s _D/O1s _L area ratios of the 15 Mn/Al catalysts with respect to calcination temperature was 900 > 500 > 700 °C, which was in good agreement with that observed for the catalytic activity. In addition, the activity order of the 15 wt% Mn-supported catalysts with respect to the type of support was γ-Al₂O₃ > SiO₂ > TiO₂. The 15 wt% Mn/Al catalyst, which had a higher O1s _D/O1s _L area ratio, showed better activity than the 15 wt% Mn/SiO₂ (15 Mn/Si) and 15 wt% Mn/TiO₂ (15 Mn/Ti) catalysts. Defect oxides played a significant role in the catalytic oxidation of VOCs. The catalytic activity with respect to the type of VOC decreased in the order of benzene > toluene > o-xylene.     

Fast procedure for self-absorption correction for low γ energy radionuclide 210Pb determination in solid environmental samples

Low-energy X and γ radiations (for example of ²¹⁰Pb: E _γ = 46.5 keV) are effectively self-absorbed even in thin environmental samples, including air filters with captured dust or contaminated soil, as well as in bottom sediment matrixes with limited quantities of the samples. In this paper, a simple method for the direct analysis of ²¹⁰Pb (T _1/2 = 22.3 years) by gamma-ray spectrometry in environmental samples with self-absorption correction is described. The method is based on the comparison of two γ peak activities coming from other natural radionuclides, usually present in environmental samples. We have analyzed the dependence of the self-absorption correction factor for the ²¹⁰Pb activity on the activity ratios of 911 and 209 keV peaks and 609 and 295 keV peaks coming from nuclides of ²³⁸U or ²³²Th rows, present in typical environmental samples.     

(Na0.74Ag1.26)BaSnS4: A New AgGaS2-Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold

The development of high-power solid-state lasers is in urgent need of infrared (IR) nonlinear optical (NLO) materials with wide band gaps and high laser-induced damage thresholds (LIDTs). Herein, a new compressed chalcopyrite-like IR NLO crystal (Na_0.74Ag_1.26)BaSnS₄ was successfully synthesized using a facile high-temperature solid-state method. Its structure can be considered as a variant of chalcopyrite AgGaS₂ (AGS)-type ones. It features a three-dimensional framework constructed by corner-sharing {[(Na/Ag)S₄]⁷⁻}_∞ layers and isolated SnS₄ tetrahedra with negative cavities occupied by counter ion Ba²⁺. (Na_0.74Ag_1.26)BaSnS₄ exhibits phase-matchable moderate SHG response (0.31 × AGS), wide band gap (3.70 eV), and high LIDT (6.44 × AGS). Theoretical calculations reveal that the NLO response of (Na_0.74Ag_1.26)BaSnS₄ is mainly originated from the synergetic effects of AgS₄ and SnS₄ tetrahedra, and the inclusion of alkaline and alkaline earth metals is responsible for the wide band gap and high LIDT. Moreover, the discovery of this chalcopyrite-like compound will provide a feasible design strategy for the exploration of new promising IR NLO materials.     

Transition between direct gap and indirect gap in two dimensional hydrogenated honeycomb Si x Ge1−x alloys

Using first-principles calculations, we have explored the structural and electronic properties of fully hydrogenated honeycomb Si _x Ge_1?x H alloys. Finite band gaps are opened by hydrogenation for x in the whole range from 0 to 1, while their nature and values can be tuned by x. When x is <0.7, the band gap is direct (from Γ to Γ). And when x is ≥0.7, the gap turns into indirect (from Γ to M). For all the computed compositions, the two kinds of energy differences between valence band and conduction band, Γ–Γ and Γ–M, are described well by two polynomial functions of x. The smaller of the two functions gives a good prediction for the overall band gap at any x. The two curves cross at x = 0.7, leading to the change of band gap type. At PBE level, the values of band gap for different x spread from 1.09 to 2.29 eV. These findings give a new route to tune the electronic properties of these materials and may have potential applications in nanoscale optoelectronics.     

Exploration of nonlinear optical behavior in asymmetric dithieno [3,2b:2′,3′d] pyrrole based push pull constrain: A theoretical approach

The organic compounds with end-capped acceptors obtained much consideration in optoelectronic field owing to their promising electronic properties. Herein, a series of PTMD1-PTMD6 conjugated compounds having D-π-A architecture were designed via structural tailoring including end-capped acceptors in non-fullerene compound (PTMR). The PTMR and its designed compounds were used at M06/6-311G(d,p) level for their optimization analysis and subsequently, by using optimized geometries to perform non-linear optical (NLO), frontier molecular orbitals (FMOs) and natural bond orbitals (NBOs) analyses. The quantum chemical investigations revealed that all the designed compounds showed significant reduction in band gaps with the range of 1.467–1.880 eV in comparison to PTMR (2.308 eV). The band gaps were found as PTMR (2.308) > PTMD6 (1.880) > PTMD1 (1.752) > PTMD2 (1.693) > PTMD4 (1.532) > PTMD5 (1.514) > PTMD3 (1.467) with eV in the descending order. Further, density of states (DOS) supported the results of FMOs study, consequently, according to transition density matrix (TDMs), the designed chromophores (PTMD1-PTMD6) displayed the transmission of charge effectively. The PTMD3 showed the maximum value of λ_max at 764.627 nm as compared to all the designed derivatives with greater bathochromic shift. The compound PTMD3 showed the highest values of β_tot and < γ > among all the studied compounds i.e., 7.695 × 10^-27 and 1.776 × 10^-31 esu, respectively. According to theoretical investigation, the structural modification with different acceptor moieties played an important role in the context of desirable NLO materials for optoelectronic applications.     

Synthesis, growth, thermal, optical, mechanical and dielectric studies of N-succinopyridine

Organic nonlinear optical (NLO) material, N-succinopyridine (NSP), was synthesised and bulk single crystals were grown from aqueous solution using isothermal solvent evaporation technique. The stoichiometric form of NSP has been confirmed by carbon–hydrogen–nitrogen analysis. NSP crystallizes in orthorhombic system with non-centrosymmetric space group P2₁2₁2₁ and unit cell dimensions a = 7.721(2) Å, b = 7.762(3) Å, c = 14.951(3) Å. The thermal stability, thermal decomposition and specific heat capacity of NSP have been investigated by thermogravimetric/differential thermal analysis, differential scanning calorimetric (DSC) analysis and modulated DSC analysis. A wide transparency window, 294–1,100 nm, useful for optoelectronic applications is indicated by UV–Vis–NIR studies. The NLO second harmonic generation efficiency analysis using Nd:YAG laser (1,064 nm) revealed that the SHG efficiency of NSP is about 1.2 times higher than that of standard potassium dihydrogen phosphate powder of comparable size and more importantly that it is phase-matchable. The room temperature mechanical behaviours of NSP have been tested using Vicker’s microhardness tester and the results were analysed through classical Mayer’s law. The dielectric behaviours such as dielectric constant, dielectric loss and ac conductivity of NSP single crystal have also been investigated as a function of frequency (20 Hz–1 MHz) and temperature (308–358 K).     

Dioxaborine- and indole-terminated polymethines: effects of bridge substitution on absorption spectra and third-order polarizabilities

Cyanine-like dyes are promising candidates for third-order nonlinear optical (NLO) applications such as all-optical switching. Here, we examine the consequences for linear and nonlinear optical properties of varying substituents on the central methine unit of bis(dioxaborine)-terminated anionic pentamethines and bis(indole)-terminated cationic heptamethines. The variation in absorption maxima and electrochemical potentials with structure can generally be rationalized using the Dewar-Knott rules, providing that mesomeric and inductive electron-withdrawal and donation are explicitly considered. In the case of nitro- and (dioxaborinyl)vinyl-substituted bis(dioxaborine) pentamethines, the low-energy transitions are significantly broadened, consistent with (1)H NMR spectra indicating deviation from cyanine-like geometry. Real and imaginary parts of the third-order polarizabilities, Re(γ) and Im(γ), were measured at 1.3 μm. The values of Im(γ) indicate that the values of Re(γ) are significantly resonantly enhanced, while the positive value of Re(γ) found for a nitro-substituted dioxaborine example is atypical for a symmetrical polymethine and suggests that a two-state treatment is inadequate. The relevance of these results to chromophore design for third-order NLO applications is discussed.     

An Eicosanuclear Heterothiometallic Mo/S/Cu Cluster: Synthesis and Third-Order Nonlinear Optical Property

A potassium-crownether host–guest cation-templated synthetic method was used to build a heterothiometallic Mo/S/Cu cluster {[(K ? dibenzo-18-crown-6)(NMP)₂]₂[(K ? dibenzo-18-crown-6)(NMP)]₂[Mo₈S₃₂Cu₁₂]·H₂O} (1). 1 was structurally determined by X-ray single crystal and powder diffractions. The anionic Mo/S/Cu cluster [Mo₈S₃₂Cu₁₂]^4? exhibits a unique octameric eicosanuclear supra-cubane-like architecture. Potassium-crownether cations show “satellite-receiver”-shaped and hexagonal-pyramidal configurations. Moreover, the third-order nonlinear optical (NLO) property was studied through Z-scan method (532 nm, 4 ns pulses), which reveals that 1 possesses effective NLO absorptive and refractive properties.     

Comparison and correlation of in vitro, in vivo and in silico evaluations of alpha, beta and gamma cyclodextrin complexes of curcumin

In the present study investigated the effect of curcumin (CUR) alpha (α), beta (β) and gamma (γ) cyclodextrin (CD) complexes on its solubility and bioavailability. CUR the active principle of turmeric is a natural antioxidant agent with potent anti-inflammatory activity along with chemotherapeutic and chemopreventive properties. Poor solubility and poor oral bioavailability are the main reasons which preclude CUR use in therapy. Extent of complexation was β-CD complex (82 %) > γ-CD (71 %) > α-CD (65 %). Pulverization method resulted in significant enhancement of CUR (0.002 mg/ml) solubility with CUR α-CD complex (0.364 mg/ml) > CUR β-CD complex (0.186 mg/ml) > CUR γ-CD complex (0.068 mg/ml). Gibbs-free energy and in silico molecular docking studies favour formation of α-CD complex > β-CD complex > γ-CD complex. With reference to CUR, relative bioavailability of CUR α-CD, CUR β-CD and CUR γ-CD complexes were 460, 365 and 99 % respectively. CUR–CD complexes exhibited increased bioavailability with an increase in t_½, tmax, Cmax, AUC, Ka, and MRT; and a decrease in Ke, clearance and Vd values. AUC increase was CUR α-CD complex > CUR β-CD complex > CUR γ-CD complex. Significant difference (p < 0.05) was observed between CUR α-CD complex and CUR γ-CD complex by one-way ANOVA and Dunnett’s post hoc test for multiple comparison analysis. Correlation observed between in vitro, in vivo and in silico methods indicates potential of in silico and in vitro methods in CD selection.     

Thermal studies and decomposition kinetics of alkaline earth metal trichloroacetates

Alkaline earth metal trichloroacetates M(O₂CCCl₃)₂·nH₂O, where M = Be (1), n = 4; M = Mg (2), n = 6; M = Ca (3) or Sr (4) or Ba (5), n = 4, were synthesized and their thermal behavior analyzed using thermogravimetric analysis (TG/DTG/DSC). A critical examination was made for the apparent activation energy by means of non-isothermal kinetic methods employing multiple heating rates. A systematic and comparative study of thermal decomposition was carried out at different heating rates i.e., 5, 10, 15, and 20 °C min^?1 for various trichloroacetates synthesized. It was observed that the Ca, Sr, and Ba trichloroacetates decompose preferentially to respective metal halides while Be and Mg compounds decompose to metal and metal oxide, respectively. The composition of the final residues was also confirmed using FT-IR spectroscopy. The activation energy follows the order: Mg > Ca > Sr > Ba, Be being the exception. Results reveal that each metal trichloroacetate decomposes through its unique thermolysis mechanism.     

Energetic of molecular interface at metal-organic heterojunction: the case of thiophenethiolate chemisorbed on Au(111)

To probe the cooperativity of charge transfer between organoimido and hexamolybdate, and enhance the second-order nonlinear optical (NLO) response of organoimido derivatives of hexamolybdates, electronic structures and second-order NLO properties of a series of charge-transfer covalently bonded organoimido derived hexamolybdate complexes with donor-(π conjugated bridge)-acceptor-(π conjugated bridge)-donor or acceptor-(π conjugated bridge)-donor-(π conjugated bridge)-acceptor structures were studied by density functional theory. Studies show that different combinations of the donor, acceptor, heterocycle, –C≡C– and –N=N– moieties, and orientation of heterocycle remarkably affect the second-order NLO responses. The complexes containing electronic acceptor matched with the direction of charge transfer possess remarkable large molecular second-order polarizabilities. Electronic transitions to crucial excited states show that x-polarized transition, contributed to the off-diagonal second-order polarizabiliy tensor (β_zxx), possesses lower excited energy compared with z-polarized transition which accounted for the diagonal second-order polarizabiliy tensor (β_zzz) and thus led to the large in-plane nonlinear anisotropy (u = β_zxx/β_zzz) value, as well as good two-dimensional (2-D) second-order NLO properties. These complexes can be used as excellent 2-D second-order NLO materials from the standpoint of both large β and u values.     

Thermal analysis, decomposition kinetics, and molecular modeling of transition metal (Fe, Co) surfactant complexes

A detailed thermal analysis of iron and cobalt surfactant complexes of the type [M(CH₃COO)₄]^2?[C₁₂H₂₅NH₃ ⁺]₂ has been carried out using Thermogravimetric (TG) analysis at different heating rates (i.e., 5, 10, 15, and 20 °C min^?1). It has been observed that iron complex decomposes by a different mechanism compared to other transition metal complexes. Metal is the final product instead of metal oxide. Combining the results from our previous study, first row transition metal complexes exhibit an order of stability in agreement with the famous Irving Williams series, i.e., the apparent activation energy, E for thermal decomposition varies as: E _Fe > E _Co < E _Ni < E _Cu > E _Zn (exception being iron because of different decomposition mechanism). Thermal decomposition parameters have been measured and compared using the multiple heating rate method of Flynn–Wall–Ozawa. Further, molecular modeling calculations have been carried out to compare the experimental TG data with theoretical computations for the synthesized metal surfactant complexes. Minimum energy optimized structures for the complexes have been obtained using Gaussian software.