Substituents destabilize the molecule by increasing biradicaloid character and stabilize by intramolecular charge transfer in the derivatives of benzobis(thiadiazole) and thiadiazolothienopyrazine: a computational study

Keeping in view the possible applications of singlet open-shell molecules as semiconductors, non-classical derivatives of the heterocyclic rings benzobis(thiadiazole) (BBT) and its positional isomer thiadiazolothienopyrazine (TTP) are characterized using DFT methodologies. M06-2X, B3LYP and BHandHLYP functionals were used to optimize the geometries and estimate the vertical transition energies. It is observed that unlike the BHandHLYP functional (50% exchange), which gives rise to spin-contaminated solutions for all molecules in the series, M06-2X (54% exchange) affords a wavefunction either with no instability or negligible instability for most of the molecules. The results are compared with the earlier reported experimental data and those obtained herein using the spin-flip (SF)-5050 method. It is found that B3LYP does not fare well while on the other hand the M06-2X and SF-50-50 are in good agreement with the experimental results. It is seen that M06-2X TD-DFT for the molecules can be carried out without major spin contamination and also that the more time-consuming CI can be avoided for the calculation of transition energies. The biradical nature of the molecules is estimated by the singlet-triplet gap. Intramolecular charge transfer is calculated. It is found that the ring substituents donate charge in the ground state, creating a zwitterionic structure. Thus the substituents play an interesting dual role, decreasing the stability of the molecule by increasing the biradical character (small HOMO-LUMO gap), and stabilization of this ground state by intramolecular charge transfer.     

Magnetism and the biradicaloid character of π-aromatic and antiaromatic systems in a strong magnetic field

The previously developed scheme of the full configuration interaction for magnetic perturbations of π systems is transformed into a scheme for calculations in the finite field. It helps create “magnetic portraits” of molecules, reflecting the essentially non-linear behavior of conjugated systems in a strong field. In particular, possible latent paramagnetism of aromatic systems and correspondingly latent diamagnetism of antiaromatic ones is easily detected. The degree of the π electron shell openness as well as the singlet-triplet splitting in the field are evaluated. From the data obtained it follows that in the strong magnetic field an aromatic molecule becomes as a rule biradicaloid and non-aromatic. Accordingly, an antiaromatic system dramatically reduces its initial biradicaloid character and thus loses its antiaromaticity.     

Structural,optical, and charge transport properties of cyclopentadithiophene derivatives: a theoretical study

Density functional theory calculations were carried out to investigate the structural and opto-electronic properties of cyclopenta[2,1-b:3,4-b′]dithiophene (CPDT) derivatives. The ground state, cationic and anionic geometries of cyclopentadithiophene derivatives were optimized at B3LYP/6-311G(d,p) level of theory. Based on these geometries, ionic state properties such as ionization potentials, electron affinities, hole extraction potential, and electron extraction potential of cyclopentadithiophene derivatives have been calculated. The charge transfer integral, spatial overlap integral, and site energy were calculated from the matrix elements of Kohn–Sham Hamiltonian. Computed results show that the mobility of charge carriers in CPDT derivatives is strongly affected by the substitution of electron withdrawing group at bridge-head and α-positions. The excited state geometry of CPDT derivatives were optimized using configuration interaction singles method. On the basis of ground and excited states geometry, absorption and emission spectra of cyclopentadithiophene derivatives were calculated using the time-dependent density functional theory method. It has been observed that the substitution of EWG in cyclopentadithiophene core alters the absorption and emission spectra. The nonlinear optical property of CPDT derivatives have been studied through computed static polarizability and first hyperpolarizability.     

Nucleophilic character of a charge neutral, high oxidation state d0 zirconium trimethylenemethane complex

The nucleophilic character of a charge neutral, high oxidation d0 zirconium trimethylenemethane (TMM) class of compound of general structure Cp*Zr(TMM)[N(R1)C(Me)N(R2)], 1a (R1 = R2 = i-Pr) and 1b (R1 = t-Bu, R2 = Et), is presented through documentation of its reactivity with a range of alkyl and silyl halides and triflates, including unactivated ones such as ethyl triflate. These results should contribute to efforts directed toward expanding the synthetic chemist's toolbox of synthetic methods for the construction of complex organic molecules.     

Theoretical design of the biradical character in 1,3-diphosphacyclobutanediyl and homologous structures

The electronic nature of 1,3-diphosphacyclobutane-2,4-diyl is explored with wavefunction based and density functional methods. According to MCSCF calculations the singlet state of the title compound is a biradicaloid with closed shell character, the number of unpaired electrons, assigned upon the analysis of the natural orbitals, is close to one. The participation of closed shell contributions in the overall wavefunction arises from a strong mixing of canonical structures, which emphasizes (a) the phosphorane type of bonding as well as (b) π-delocalization within the ring system. The bonding situation changes when σ-attracting substituents, e.g. amino groups, are attached to the phosphorus atoms. They inhibit possible cyclic π-delocalization and enhance the biradical character within the ring system.     

Ab initio study of a biradical radiationless decay channel of the lowest excited electronic state of cytosine and its derivatives

A theoretical model for the ultrafast S1-->S0 internal conversion of cytosine is presented, in which a state switch from the initially prepared 1pipi* state to the out-of-plane deformed excited state of biradical character controls the rate of the S1(1pipi*) decay. This mechanism successfully accounts for the dramatically longer S1 lifetimes of 5-fluorocytosine and N-acetylcytosine relative to cytosine. The replacement of the C5 hydrogen atom by a methyl group is predicted to lead to a substantial, but not dramatic, increase in the S1 lifetime, also consistent with experiment. It is this ability to correctly predict the substituent effects that distinguishes the present model from the previously proposed mechanisms.     

The distribution of electronic charge in the ground state of cubic boron nitride

The distribution of electronic charge in cubic boron nitride is investigated using the bond orbital wave functions recently calculated by Coulson and Doggett. Plots of the one-electron density function, in the (110) plane, are found to be insensitive to the choice of atomic basis functions, in contradistinction to the previously calculated effective atomic charges. A number of structure amplitudes are also calculated for each of the bond orbital wave functions.     

Orbital symmetry,orbital stability,and orbital pairing rules for organic reactions in the ground state

A generalization of the Hartree–Fock molecular orbital (MO) theory for treating diradical intermediates was explained pictorially by drawing molecular orbitals of diradical species such as ring-opened trimethylene. The generalized MO theory applied to elucidate electronic mechanisms of concerted, ionic, radical, and ion-radical reactions of organic reactants in the ground state. Generalized MO computations revealed the most essential characteristics of these reactions and mutal relationships between the worlds of Woodward–Hoffmann and Hughes–Ingold. Generalized MO studies supported our orbital symmetry, stability and pairing rules for concerted, ionic and radical reactions in the ground state, respectively. An extension of MO treatments to excited states reactions was briefly pointed out in relation to the density and spin correlation functions by the multireference CI wave functions.     

Application of the direct configuration interaction method to the ground state of O2

The Direct Configuration Interaction Method, originally due to Roos [1], has been implemented using the method of Lucchese and Schaefer [2], for open shell systems. As in the closed-shell case, the method is very efficient. Results are presented for a part of the potential energy curve of the O₂ ^3– _g ground state electronic configuration, together with several properties.     

A new parameter to control heat transport in nanofluids: surface charge state of the particle in suspension

Although various conjectures have been proposed to explain the abnormal increase in thermal conductivity of nanofluids, the detailed mechanism has not been fully understood and explained. The main reason is due to the lack of knowledge of the most fundamental factor governing the mechanisms such as Brownian motion, liquid layering, phonon transport, surface chemical effects, and agglomeration. Applying a surface complexation model for the measurement data of hydrodynamic size, zeta potential, and thermal conductivity, we have shown that surface charge states are mainly responsible for the increase in the present condition and may be the factor incorporating all the mechanisms as well.     

Role of excited state intramolecular charge transfer in the photophysical properties of norfloxacin and its derivatives

The photophysical properties of 1-ethyl-6-fluoro-7-(1-piperazinyl)-1,4-dihydro-4-oxoquinoline-3-carboxylic acid (norfloxacin, NFX) and some of its derivatives have been studied to evaluate the role of the free carboxylic acid and the nonprotonated piperazinyl group in the behavior of the 1,4-dihydro-4-oxoquinoline ring. Steady state and time-resolved fluorescence measurements at different pHs provide clear evidence in favor of singlet excited-state deactivation of NFX and its N(4')-methyl derivative pefloxacin (PFX) via intramolecular electron transfer from the N(4') atom of the piperazinyl ring to the fluoroquinolone (FQ) main system. This is a very efficient, energy-wasting pathway, which becomes dramatically enhanced in basic media. Acetylation at N(4') (as in ANFX) decreases the availability of the lone pair, making observable its fluorescence and the transient absorption spectrum of its triplet excited state even at high pH. It also reveals that the geometry of FQs changes from an almost sp3 hybridization of the N(1') of the piperazinyl substituent in the ground state to nearly sp2 in the singlet excited state (rehybridization accompanied by intramolecular charge transfer, RICT); accordingly, the singlet energy of ANFX is significantly lower than that of NFX and PFX. The fluorescence measurements using acetonitrile as a polar nonprotic organic solvent further support deactivation of the singlet excited state of nonacetylated NFX derivatives via intramolecular electron transfer from the N(4') atom.     

Crystal packing and charge transport in single crystals of chrysene derivatives: Impact of halogenation

Crystal packing has strong influence on the charge mobility for organic semiconductors, so the elucidation of the structure-property relationship is important for the design of high-performance organic semiconductors. Halogen substitution has been shown to be a promising strategy to alter the crystal structure without significantly changing the molecular size in previous reports. This paper studies the influence of halogenation on charge transport in single crystals of chrysene derivatives from a theoretical standpoint. The structure-property relationship is first rationalized by investigating the reorganization energy and electronic coupling from the density functional theory calculations. Based on the Marcus charge transfer theory, the mobilities in the molecular monolayer are then calculated with the random walk simulation technique from which the angular resolution anisotropic mobilities are obtained on the fly. It is shown that the mobilities become much larger for holes than those for electrons in the molecular monolayer when the halogenation occurs. Furthermore, the intra-layer charge transport is little influenced by the inter-layer pathways in the single crystals of the halogenated chrysene derivatives, while the opposite case is shown for the crystal of the nonhalogenated chrysene derivative. The reason for the variations of charge transport is discussed theoretically.     

Molecular structure,conformational stability,energetic and intramolecular hydrogen bonding in ground,and electronic excited state of 3-mercapto propeneselenal

In the present work, a conformational analysis of 3-mercapto propeneselenal is performed using several computational methods, including DFT (B3LYP), MP2, and G2MP2. At the DFT and G2MP2 levels the most stable conformers of title compound are characterized by an extended backbone structure, minimizing the steric repulsions between the sulfur and selenium lone pairs. Two conformers exhibit hydrogen bonding. This feature, although not being the dominant factor in energetic terms, appears to be of foremost importance to define the geometry of the molecule. The influence of the solvent on the stability order of conformers and the strength of intramolecular hydrogen bonding was considered using the PCM, SCI–PCM, and IEF–PCM methods. The results of analysis by quantum theory of “Atoms in Molecules” and natural bond orbital method fairly support the DFT results. The calculated HOMO and LUMO energies showed that charge transfer occurs within the molecule. Further verification of the obtained transition state structures was implemented via intrinsic reaction coordinate analysis. Calculations of the ¹H NMR chemical shift at GIAO/B3LYP/6–311++G** levels of theory are also presented. The excited-state properties of intramolecular hydrogen bonding in hydrogen-bonded systems have been investigated theoretically using the time-dependent density functional theory method.     

Definitive evidence for the contribution of biradical character in a closed-shell molecule, derivative of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene

This study provides conclusive proof that the thermally excited open-shell state with biradical character is contributing to the ground state of a closed-shell molecule, tF-BDPI-2Y, where four hydrogen atoms at the central phenylene ring are substituted with four fluorine atoms of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene (BDPI-2Y). A small increase in the population of biradical species of tF-BDPI-2Y results in the formation of the dimer form by the radical recombination reaction. Controlling the equilibrium between a closed-shell diamagnetic-quinoid state and an open-shell paramagnetic-biradical state will provide significant progress in the field of pi-conjugated delocalized biradical chemistry.     

Enhancing the healing ability and charge transport thermal stability of a diketopyrrolopyrrole based conjugated polymer by incorporating coumarin groups in the side chains

In this paper, we present a new design strategy for healable polymeric semiconductors, which are demanding for the future flexible electronics, by incorporating coumarin groups in the polymer side chains. The selection of coumarin groups is based on the fact that photo-dimerization can occur to coumarins upon UV light irradiation, thus side chains of conjugated polymers with coumarins can be cross-linked. The photo-crosslinking of side chains has negligible effect on the thin film morphology and interchain packing order for the DPP-based conjugated polymer PDPP4T-DCM with coumarins in the side chains. However, the photo-crosslinking can facilitate the repair of the mechanically damaged thin film of PDPP4T-DCM and the recovery of the semiconducting properties. Additionally, the photo-crosslinking due to the coumarins in the side chains can lock thin film morphology and thus improve the thermal stability of charge transport.     

On the ground state of titanium phosphide, TiP: a theoretical investigation

Using multireference variational and coupled cluster methods in conjunction with very large core-correlation-consistent basis sets, we have confirmed that the ground state of TiP is of (2)Sigma(+) symmetry with the first excited state A (2)Delta no more than 3.5 kcal/mol higher. We also report full potential energy curves, dissociation energies, bond lengths, dipole moments, and the usual spectroscopic constants.     

Charge resonance character in the charge transfer state of bianthryls: effect of symmetry breaking on time-resolved near-IR absorption spectra

We study the effects of symmetry breaking on the photogenerated intramolecular charge transfer (CT) state of 9,9'-bianthryl (BA) with femtosecond time-resolved near-IR spectroscopy. The time-resolved near-IR spectra are measured in acetonitrile for a symmetric substituted derivative of 10,10'-dicyano-9,9'-bianthryl (DCBA) and asymmetric substituted derivatives of 10-cyano-9,9'-bianthryl (CBA) and 9-(N-carbazolyl)anthracene (C9A), as well as nonsubstituted BA. The transient near-IR absorption spectrum of each compound at 0 ps has a locally excited (LE) absorption band, which agrees with the transient absorption band of the corresponding monomer unit. At 3 ps after the photoexcitation, the symmetric compounds show a broad charge transfer (CT) absorption band, whereas no absorption peak appears in the spectra of the asymmetric compounds. The broad CT absorption at 1250 nm only observed for the symmetric compounds can be attributed to the charge resonance transition associated with two equivalent charge separated states.     

Suppressing the thermal metacyclophanediene to dihydropyrene isomerization: synthesis and rearrangement of 8,16-dicyano[2.2]metacyclophane-1,9-diene and evidence supporting the proposed biradicaloid mechanism

Synthesis of 8,16-dicyano-anti-[2.2]metacyclophane-1,9-diene, 1b, was achieved in five steps from 1,3-bis(bromomethyl)benzonitrile. Unlike most metacyclophanedienes which easily thermally isomerize (tau 1/2 = minutes to days at 20 degrees C) to dihydropyrenes 2, dinitrile 1b shows no tendency to convert thermally to 2b at room temperature (tau 1/2 > 30 years), consistent with predictions based on calculation of activation barriers. Irradiation of cyclophanediene 1b with UV light readily forms the dinitriledihydropyrene 2b, which unexpectedly shows a much more facile (50 degrees C) 1,5-sigmatropic rearrangement of the internal nitrile groups to give dihydropyrenes 9b and then 10b than is the case for internal methyl substituents, 2a, which forms 9a at temperatures above 190 degrees C. Synthesis of the 2-formyl derivative 1c and the 2-naphthoyl derivative 1d are also described. These substituents were predicted to lower the activation barrier for the thermal closing reaction to the corresponding dihydropyrenes, and experimental evidence supports these calculations.     

Determination of the ground state,excited state and change in dipole moments of magnesium and zinc chlorin

High-resolution Stark effect measurements on the S1 <-- S0 (pi pi*) origin of magnesium chlorin (MgCh) and zinc chlorin (ZnCh) in single crystals of n-octane at 4.2 K are reported. The corresponding change in dipole moment (absolute value(delta mu(ge))) associated with each transition was estimated to be 0.23 +/- 0.04 and 0.27 +/- 0.05 debye, respectively. Each molecule's orientation in the n-octane crystal was also determined. The change in dipole moment of MgCh was also found using solvatochromic shift data (absolute value(delta mu(ge))) = 0.33 +/- 0.08 debye). The ground state dipole moment (mu(g)) of MgCh was determined by dielectric constant measurement of MgCh/benzene solutions (mu(g) = 2.26 +/- 0.08 debye). These were combined to calculate the average excited state dipole moment of MgCh (mu(e) = 2.51 +/- 0.08 debye). The ground state dipole moment of ZnCh was also determined using solvatochromic shift data (mu(g) = 3.17 +/- 0.08 debye). This was combined with its measured absolute value(delta mu(ge)) to calculate the excited state dipole moment of ZnCh (mu(e) = 3.44 +/- 0.08 debye); the S1 <-- S0 (pi pi*) origin band of both complexes was red-shifted at room temperature as the polarity of the solvents was increased, which implies that delta mu(ge) is positive.     

Spatially resolved concentration studies of ground state atoms in a flame: saturated absorption spectroscopic method

The authors describe the application of the saturated absorption spectroscopic method, introduced by Goldsmith, Optics Letters6, 525 (1981), to the determination of spatially resolved concentrations of ground state atoms in a flame. In the described version of the method, the beam of a single pulsed dye laser is divided into a probing and a disturing (= saturating beam), which intersect in a small volume of the flame. The perturbance of the probing beam by the saturating beam is a function of the concentration of the absorbing species. The authors foresee this method to become an important tool for flame and plasma diagnostic studies.