Two-photon absorption properties of two-dimensional π-conjugated chromophores: combined experimental and theoretical study

The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis.     

Controlled rearrangement of lactam-tethered allenols with brominating reagents: a combined experimental and theoretical study on α- versus β-keto lactam formation

N-Bromosuccinimide (NBS) smoothly promotes the ring expansion of lactam-tethered allenols to efficiently afford cyclic α- or β-ketoamides with good yields and high chemo-, regio-, and diastereoselectivity, through controlled C-C bond cleavage of the β- or γ-lactam nucleus. Interestingly, in contrast to the rearrangement reactions of 2-azetidinone-tethered allenols, which lead to the corresponding tetramic acid derivatives (β-keto lactam adducts) as the sole products, the reactions of 2-indolinone-tethered allenols under similar conditions give quinoline-2,3-diones (α-keto lactam adducts) as the exclusive or major products. To rationalize the experimental observations, theoretical studies have been performed.     

Reaction of a chlorovinylcarbene with ketenealkyl silyl acetals. Synthesis of new α- and β-allenic carboxylates.

The reaction of ketenealkylsilylacetals with 1,1-dimethyl-2,2,3-trichlorocyclopropane in the presence of methyllithium leads to cyclopropane compounds, which, when treated with tetrabutylammonium fluoride give α- or β-allenic carboxylates.     

Quantum chemical properties investigation and molecular docking analysis with DNA topoisomerase II of β-carboline indole alkaloids from Simaba guianensis: a combined experimental and theoretical DFT study

Structural Chemistry - A theoretical and experimental DFT study of the vibrational, structural, and quantum properties of 9-methoxy-canthin-6-one (I) and...     

Formation and structure of Co₂O₄: a combined IR matrix isolation and theoretical study

The formation and structure of dicobalt tetroxide (Co?O?) has been investigated using matrix isolation in solid neon and argon coupled to infrared spectroscopy and quantum chemical methods. It is found that Co?O? can be formed by dimerization of cobalt dioxide without activation energy by diffusion of ground state CoO? molecules at 9 K in the dark. The IR data on eight fundamentals, isotopic effects and quantum chemical calculations are both consistent with a centro-symmetrical structure with two pairs of equivalent oxygen atoms, engaged in a stronger terminal Co-O bond and in a weaker bridging Co-O-Co position. Evidence for other, metastable states is also presented, but the data are not conclusive. The electronic structure and formation pathway has been investigated using the Tao-Perdew-Staroverov-Scuseria/triple-zeta valence polarived basis set (TPSS/TZVP) and broken symmetry unrestricted density functional theory (BS-UDFT) approach and the ground electronic state is predicted to be an open shell 1Ag singlet with the quintet, triplet, septet, and nonet states above by 3.3, 4.9, 9.3, and 27.7 kcal/mol, respectively, but certainly has a complex multireference character that hinders the use of more precise multireference approaches. Different formation pathways have been considered, and the 2(O═Co═O) → Co?O? dimerization reaction is found to be the only barrierless channel and to be strongly exothermic. Comparisons with another transition metal (TM) oxide system (V?O?) suggests that the difference in predicted ground state geometries in TM?O? systems might be due in HOMO-LUMO shapes of the isolated dioxide subunits and optimal overlap configurations.     

Pyrazolium- and 1,2-cyclopentadiene-based ligands as σ-donors: a theoretical study of electronic structure and bonding

A high-level theoretical investigation of 1,2-cyclopentadiene (4) was performed using density functional theory and wave function methods. The results reveal that, in contrast to earlier assumptions, the ground state of this ephemeral "allene" is carbene-like with a small diradical component. Furthermore, the electronic structure and chemistry of 4 are found to parallel that of 1,2,4,6-cycloheptatetraene: both molecules possess a low-lying excited singlet state with a closed-shell carbenic structure, enabling rich coordination chemistry. Energy decomposition analyses conducted for currently unknown metal complexes of 4 as well as those involving stable carbenes based on the pyrazolium framework (aka "bent allenes" or remote N-heterocyclic carbenes) indicate that all investigated ligands form particularly strong metal-carbon bonds. Most notably, without exocyclic π-type substituents, 4 and pyrazolin-4-ylidenes are the strongest donor ligands examined, in large part because of the energy and shape of their highest occupied molecular orbital. As a whole, the current work opens a new chapter in the chemistry of 1,2-cyclopentadiene, which is hoped to spark renewed interest among experimentalists. In addition, results from the conducted bonding analyses underline that more emphasis should be placed on purely carbocyclic carbenes as unprecedented σ-donor strengths can be realized through this route.     

Synthesis and theoretical study of first generation CCK-functional dendrimers

A convenient synthesis and theoretical study of five CCK-functional dendrimers is described.The dendritic cores were linked with the CCK(Trp-Met-Asp(OBn)-PheNH2) fragment by forming amide bonds to give five target molecules.The structures of CCK-functional dendrimers were characterized by NMR,MS spectrum and predicted using molecular mechanics and PM3 semi- empirical molecular orbital theory.     

Sodium dialkyl-amidozincates: alkyl or amido bases? An experimental and theoretical case study

Alkali metal zincate reagents are attracting considerable attention at present in respect to their often special reactivity/selectivity in hydrogen-metal and halogen-metal interconversion reactions. Heteroleptic diorgano-amidozincates, typified by lithium di-tert-butyltetramethylpiperidinozincate, have proved to be especially useful reagents in such applications. In this paper the related sodium TMP-zincate, prepared as its TMEDA (N,N,N',N'-tetramethylethylenediamine) adduct, [TMEDA.Na(mu-tBu)(mu-TMP)Zn(tBu)], 1, is introduced. This new zincate was synthesized from a 1:1:1 mixture of tBu2Zn, NaTMP, and TMEDA in hexane solution, as a colorless crystalline solid in an isolated yield of 58%. It has been characterized in solution by 1H and 13C NMR spectroscopic studies. An X-ray crystallographic study reveals that 1 adopts a five-membered (NaNZnCC) ring system featuring a TMP bridge and an unusual, asymmetrical tBu bridge involving a Na...Me agostic contact. Probing the basicity of 1, reaction with benzene affords the new hetero(tri)leptic zincate [TMEDA.Na(mu-Ph)(mu-TMP)Zn(tBu)], 2, which has also been crystallographically characterized. Thus, in this hydrogen-metal exchange reaction 1 functions as an alkyl base, with the elimination of butane, as opposed to an amido base. Also reported are DFT calculations using B3LYP functionals and the 6-311G** basis set on model zincate systems, which intimate that the preference of 1 for tBu ligand transfer over TMP ligand transfer in the reaction toward benzene is due to favorable thermodynamic factors.     

Synthesis and study of cesium-containing phosphates with a β-tridymite structure

Complex phosphates CsMg_{1 ? x} M _x PO₄ (M = Mn, Co, Cu, Zn), containing cesium and metals in the oxidation state +2, have been synthesized, and their structure and thermal behavior have been studied. Continuous solid solutions (0 ?? x ?? 1) of the ??-tridymite structure type are formed in the CsMg_{1 ? x} Mn _x PO₄, CsMg_{1 ? x} Co _x PO₄, and CsMg_{1 ? x} Zn _x PO₄ systems, whereas limited solid solutions (0 ?? x ?? 0.4) are formed in the CsMg_{1 ? x} Cu _x PO₄ system. Based on DTA data, phase transitions have been revealed in the cobalt-, copper-, and zinc-containing phosphates, and the orthorhombic or monoclinic crystal system has been identified. Unit cell parameters of the solid solutions have been calculated. Thermal expansion of the CsMPO₄ phosphates has been studied.     

α-Amino acetals containing a phosphonate or phosphine oxide group. Synthesis and reactions with resorcinols

New α-amino acetals containing a phosphonate or phosphine oxide group were synthesized by the Kabachnik-Fields reaction in the ternary system amino acetal-paraformaldehyde-dialkyl phosphonate (or dialkylphosphine oxide). Condensation of dialkyl (2,2-dimethoxyethylamino)methylphosphonates with resorcinol and its derivatives in ethanol in the presence of hydrochloric acid, apart from the corresponding 2,2-bis(polyhydroxyphenyl) ethylammonium salts, gave 2,5-bis(polyhydroxyphenyl)-1,4-bis[(dialkoxyphosphoryl)methyl]-piperazines. Dialkyl[(2,2-dimethoxyethylamino)methyl]phosphine oxides (Alk = C₈H₁₇, C₁₀H₂₁) did not react with resorcinol derivatives under similar conditions, and analogous ammonium salts were obtained by heating the reactants in boiling trifluoroacetic acid.     

Aluminum electrodeposition from a non-aqueous electrolyte—a combined computational and experimental study

Electrodeposition of aluminum (Al) from an organic non-aqueous electrolyte of ethylbenzene containing aluminum bromide is demonstrated. It is offered as a simple method for the preparation of Al coatings. This work employs distinct electrochemical techniques and explores the effects of the experimental parameters on the kinetics of the process and the quality of the final coatings. The process presented here enables deposition of pure and crystalline Al at room temperature and facilitates the production of uniform Al coatings on various metallic substrates. Morphological studies establish that the growth of Al deposits follows an island mode, and thus, the most noteworthy effect of the substrate over the morphology of the deposits originates from its impact over the nucleation stage, and the density of islands. This study is complemented by theoretical modeling for the adsorption of Al atoms at the different surfaces. Corrosion evaluation determines the dissolution mechanisms of each of the studied substrates in the examined electrolyte. These findings further corroborate the claim that this electrolyte enables the reversible electrodeposition of Al.

     

Capacity of layered cathode materials for lithium-ion batteries — a theoretical study and experimental evaluation

The theoretical capacity and the vacancy concentration of metal-ion-doped layered compounds such as LiCoO₂, LiNiO₂, and LiMnO₂, acting as cathodes in high-voltage lithium-ion batteries are calculated. The capacity shows strong dependence on valency of the doped metal ion and vacancy concentration. Experimental verification carried out to check the validity of the proposed equation for aluminium substitution into the potential layered materials shows good agreement between the experimental and theoretical capacity values. The vacancy concentration values of doped layered compounds have been found to be high when compared with that of the doped spinel compounds.     

Enantiodiscrimination of equol in β-cyclodextrin: an experimental and computational study

The interaction between the equol enantiomers and β -cyclodextrin is studied by molecular mechanics and molecular dynamics calculations. The chromatographic retention order is determined by these theoretical methods and compared with experimental findings. In the molecular mechanics calculations, the simultaneous relaxation of the host and the guest molecules is allowed, both in a vacuum and in aqueous solution. In the molecular dynamics calculations, the interaction energy between each enantiomer and the cavity is determined carrying out a simulation of 12 trajectories with different initial conditions at constant temperature (293 K), and minimising the energy of the structures extracted along the trajectories. To determine the preferential binding site and orientation of each guest molecule, the numerical density of presence in a volume element is calculated and compared with regions of maximum enantioselectivity. The more stable complex predicted in both cases is formed with R-equol, in agreement with experimental results.     

Synthesis based on β-phenylethylamines. IX. Synthesis of sulfides of β-phenylethylamines and of N-benzyltetrahydroisoquinolines

New bimolecular sulfur-containing -phenylethylamines and N-benzyltetrahydroisoquinolines have been synthesized from formyl derivatives of diaryl sulfides. The possibility of using metals as catalysts for obtaining diaryl sulfides in the reaction of ortho-substituted benzaldehydes with SCl₂ has been shown for the first time.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 731–735, September–October, 1995. Original article submitted November 11, 1994.     

Inclusion complexes of sulphanilamide drugs and β-cyclodextrin: a theoretical approach

PM3 theoretical methodology was used to access and compare the relative stability of inclusion complexes formed by sulphadiazene, sulphisomidine, sulphamethazine and sulphanilamide with β-cyclodextrin (β-CD). The study predicted that (i) the heterocyclic ring is encapsulated in the hydrophobic part and aniline ring is present in the hydrophilic part of the β-CD cavity and (ii) intermolecular hydrogen bonds were formed between host and guest molecules. The negative free energy and enthalpy changes indicated that all the four inclusion complexation processes were spontaneous and enthalpy driven process. HOMO and LUMO orbital investigation confirmed that the stability increased in the inclusion complexes and also proved no significant change in the electronic structure of the guest and host molecules after complexation.