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Alkali atom-doped hexalithioborazine (B3N3Li6-M) as a novel class of super-alkali complex has been investigated for their exceptionally high first-order and second-order electrical responsive properties. The stability of resulting complexes, B3N3Li6-M (M = Li, Na, and K), is confirmed by the ADMP simulation and the negative values of thermodynamic parameters such as binding energy (∆Eb) and Gibbs free energy (∆G). The relationship between aromaticity (NICS) and first hyperpolarizability of B3N3Li6-M follows linear relationship. Diffuse electron cloud around the central ring and doped alkali metal in the HOMO of B3N3Li6-M complexes has been attributed to the charge transfer from peripheral Li to the dopant metal (M) atom. The dipole moment of B3N3Li6-M varies between 0.507 D (M = Na) and 1.608 D (M = Li) due to charge transfer in these complexes. The mean polarizabilities (αav) of B3N3Li6-M ranging from 573.08 to 1598.86 a.u are observed. Exceptionally high value of second-order NLO parameter (βav = 5.133 × 105 a.u and βHRS = 2.166 × 106 a.u) are observed in case of Li-doped B3N3Li6 in this series. Thus, the first hyperpolarizability (βav and βHRS) values of the complexes produced by the interactions between alkali metal atoms (M) and B3N3Li6 are strong enough to demonstrate as potential second-order NLO materials. [ABSTRACT FROM AUTHOR]

Context: Quantum mechanical calculations involving electron correlation, frequency dispersion, and solvent effects were carried out to examine the second-order nonlinear optical response of various acceptor, X (-CF3, -CN, -NO2) substituted in N,N-dimethylaniline (DMA) and julolidine(JLD). Here, both DMA and JLD acts as donor and the three substituted groups, X (-CF3, -CN and -NO2) at the para position of both the ring systems as acceptor. The NLO response (βHRS) of -CF3 and -CN substituted DMA and JLD is relatively lower compared to DMA-NO2 and JLD-NO2. The charge distribution is found higher in case of -NO2 substituted DMA and JLD (±443 and ±449) compared to their -CF3 or –CN substitution. Electronic characteristics such as UV-Vis absorption spectra, crucial excited state parameters and charge transfer contribution to βHRS have been used to explain the NLO parameter of DMA-X and JLD-X. Variation of the incident optical frequency of light shows fluctuation of βHRS value and highest values of βHRS are obtain at the λmax frequency of each compound. Solvent polarity variation study on βHRS shows that βHRS varies linearly with the Kirkwood-Onsagar dielectric factor (D). Methods: All computational studies have been carried out using density functional theory (DFT) based method. Since CAM-B3LYP based hybrid functional improves the asymptotic behavior of the exchange interaction by dividing into short-range and long-range components, first hyperpolarizability values in the present study were computed using DFT/ CAM-B3LYP/ 6-31G+(d,p) level of theory. [ABSTRACT FROM AUTHOR]

The contrast of the second-order nonlinear optical response between the enol (anti and syn) and keto tautomeric equilibrium of 7-Phenyl-7H-benzo[1,2-b;4,5-b']difuran-2,3,6-trione (PBDT) with donor/acceptor substitution at the para position of phenyl group have been computed involving electron correlation, frequency dispersion, and solvent polarity effects. The Hyper Rayleigh Scattering (HRS) first-hyperpolarisability contrast between the enol and keto forms for PBDT and Nitro-substituted PBDT is 3.5 and 2.8, respectively. However, in NMe2-substituted PBDT, a large contrast (~12 times) of HRS first hyper-polarisability between enol (anti and syn) and keto form is observed. Present study reveals that electron donor group (-NMe2) in PBDT plays a pivotal role for obtaining very high contrast in the first hyper-polarisability (ßHRS and ßvec) values between the enol and keto forms compare to the electron acceptor (-NO2) group substitution at the same position. The solvent effect also plays a significant role in further improving the first hyper-polarisability value and its switching behaviour between the enol and keto forms of NMe2-PBDT. NLO switching contrast between the enol and keto forms of donor/acceptor substituted PBDT is also explained using the electronic features including UV-Vis absorption spectra, HOMO-LUMOelectron densities, optical energy gaps, charge transfer contribution etc. [ABSTRACT FROM AUTHOR]

Effect of donor–acceptor substitution position on the electrical responsive properties like polarisability, first hyper polarisability of donor–acceptor substituted azulene derivatives have been investigated using HF and Density functional theory with various hybrid functional and basis. It is observed that among the DFT methods, CAM-B3LYP hybrid functional with correlation consistent polarised triple-zeta, cc-pVTZ basis show less overestimated value of polarisability and first hyperpolarisability compare to other hybrid functional and it is again advantageous than HF with similar basis in term of its price and performance ratio. An apparent violation of minimum polarisability principle among the studied azulene derivatives are observed and it has been explain due to non-constancy of the potential functions upon substitution of donor (NMe2) and acceptor (NO2) groups at different position of azulene ring. Computed βav values are in accordance with the extent of charge transfer character of the azulene with a few exceptions. Position of donor and acceptor group at the five- and seven-member ring also play a big role in determining the electrical responsive parameter has been discussed. It is also observed that 2 and 6 carbon atom of azulene are highly sensitive towards donor acceptor substitution. [ABSTRACT FROM AUTHOR]

The effect of donor-acceptor (D-A) substituent and chain length on the electrical polarisabilities and first hyper polarisability of cis and trans biphenyl oligomeric compounds have been investigated using density functional theory-based hybrid functional CAM-B3LYP with 6-311G (2d,2p) basis set. Our extensive computational study reveals that both average polarisability and first hyper polarisability of the studied compounds increase with the increasing ethylene spacer chain length. Again the substitution of donor (NMe2) and acceptor (C≡N) at the para position of the phenyl rings to each oligomer shows order of magnitude increase of both αav and βav value compared to the unsubstituted one. This increased αav and βav values have been explained due to increasing charge transfer contribution resulting from decreasing optical energy gap (ΔE = S1 − S0) upon D-A substitution. It is also observed that the charge transfer contribution to first hyperpolarisability (βCT) is more than the polarisability (αCT) for the studied molecules. The electronic spatial extent (2>) which is a measure of electron density volume around the molecule is found to play a major role along with the intramolecular charge transfer character to explain the non-linear variation of first hyperpolarisability (βav) as a function of ethylene spacer chain length (n) and D-A substitution. [ABSTRACT FROM AUTHOR]

A novel material showing aggregation induced enhanced emission (AIEE) is developed by reprecipitation method using 2,2′ biquinoline (BQN) in aqueous medium. Morphologies of the particles are characterized using optical and scanning electron microscopic (SEM) study. The selective fluorescence and absorbance response of aggregated BQN towards Zn 2+ and H + have been explained due to ground state complexation and protonation of BQN with Zn 2+ and H + respectively. Protonated BQN exhibits charge transfer character in transoid form with yellowish green emission but in BQN-Zn 2+ complex, BQN changes to cis planer conformation and displays considerable intra ligand charge transfer (ILCT) character with sky blue color under UV excitation. A 2:1 BQN-Zn 2+ complex have been confirmed using Job’s plot. Our study revealed that BQN hydrosol act as selective turn-on fluorescence sensor for Zn 2+ ion both in acidic and alkaline medium. Further, the proton induced charge transfer character and the proposed binding modes of the receptor with Zn 2+ have been supported by DFT based computational study. [ABSTRACT FROM AUTHOR]