Promising impact of push-pull configuration into designed octacyclic naphthalene-based organic scaffolds for nonlinear optical amplitudes: a quantum chemical approach.

In opto-electronics, non-fullerene (NF) derivatives are regarded as efficient non-linear optical (NLO) materials. The present investigation was based on designing NF naphthalene-based derivatives (PCMD1-D9) with D-π-A configuration from PCMR. DFT analysis at M06/6-311G (d,p) level was accomplished to explore the photonic behavior of PCMD1-D9 compounds. Various kind of analysis like; UV-Vis, density of state (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were accomplished to understand the NLO properties of said chromophores. The configuration change led to considerable charge distribution over highest occupied and lowest unoccupied molecular orbitals with minimum band difference. The energy gap trend for all the entitled compounds was observed as; PCMD8 < PCMD5 = PCMD9 < PCMD6 < PCMD7 < PCMD4 < PCMD3 < PCMD2 < PCMD1 with the least band gap of 2.048 eV in PCMD8 among all the compounds. The UV-Visible spectrum of the entitled chromophores manifested high values of λmax in derivatives contrary to PCMR. Additionally, NBO findings explored effective intramolecular charge transfer and maximum energy of stabilization (34.31 kcal/mol) for PCMD8 chromophore. The highest linear polarizability (<α>) and dipole moment (µtot) values were exhibited by PCMD5 at 2.712 × 10-22. and 1.995 × 10-17 esu, respectively. PCMD8 push-pull configured molecular entity exhibited highest first hyper-polarizability (ßtot) at 4.747 × 10-27 esu and second hyper-polarizability at 6.867 × 10-32 esu. Overall, all the formulated chromophores exhibited significant NLO results contrary to PCMR. Hence, through this structural tailoring via various acceptors, effective NLO materials were obtained for optoelectronic applications.

Designing of banana shaped chromophores via molecular engineering of terminal groups to probe photovoltaic behavior of organic solar cell materials.

To meet the rising requirement of photovoltaic compounds for modernized hi-tech purpose, we designed six new molecules (DTPD1-DTPD6) from banana shaped small fullerene free chromophore (DTPR) by structural tailoring at terminal acceptors. Frontier molecular orbitals (FMOs), density of states (DOS), open circuit voltage (Voc), transition density matrix (TDM) analysis, optical properties, reorganization energy value of hole and electron were determined utilizing density function theory (DFT) and time-dependent density function theory (TD-DFT) approaches, to analyze photovoltaic properties of said compounds. Band gap contraction (∆E = 2.717-2.167 eV) accompanied by larger bathochromic shift (λmax = 585.490-709.693 nm) was observed in derivatives contrary to DTPR. The FMOs, DOS and TDMs investigations explored that central acceptor moiety played significant role for charge transformation. The minimum binding energy values for DTPD1-DTPD6 demonstrated the higher exciton dissociation rate with greater charge transferal rate than DTPR, which was further endorsed by TDM and DOS analyses. A comparable Voc (1.49-2.535 V) with respect to the HOMOPBDBT-LUMOacceptor for entitled compounds was investigated. In a nutshell, all the tailored chromophores can be considered as highly efficient compounds for promising OSCs with a good Voc response.

Novel Fluorinated Biphenyl Compounds Synthesized via Pd(0)-Catalyzed Reactions: Experimental and Computational Studies.

Five new difluorinated biphenyl compounds, 4'-(tert-butyl)-3,4-difluoro-1,1'-biphenyl (TBDFBP), 1-(3',4'-difluoro-[1,1'-biphenyl]-4-yl)ethanone (DFBPE), 3',4'-difluoro-2,5-dimethoxy-1,1'-biphenyl (DFDMBP), 3,4-difluoro-3'-nitro-1,1'-biphenyl (DFNBP), and (3',4'-difluoro-[1,1'-biphenyl]-3-yl)(methyl)sulfane (DFBPMS), have been successfully synthesized by the well-known Suzuki-Miyaura coupling with excellent yields averaging 78%. UV-visible, Fourier transform infrared ,and 13C NMR and 1H NMR spectroscopies along with single-crystal X-ray diffraction (SC-XRD) analysis (for TBDFBP and DFBPE) were used for the structure elucidation of the synthesized compounds. The SC-XRD results demonstrated the crystal systems of the studied compounds, TBDFBP and DFBPE, to be monoclinic, and their space groups were found to be P21/c. Also, a detailed density functional theory study was performed. The calculated structures for TBDFBP and DFBPE were found to agree quite well with the experimental results. The natural bonding orbital charge analysis suggested that molecules of these compounds should interact quite noticeably with each other in the solid phase and with polar solvent molecules. Molecular electrostatic potential analysis suggests that accumulation of positive and negative potential implies possibility of quite significant dipole-dipole intermolecular interactions in crystals of these compounds, as well as quite strong interactions with polar solvent molecules. The global reactivity parameters analysis suggests all compounds to be quite stable in redox reactions, with the compound DFNBP being relatively more reactive and the compounds TBDFBP and DFDMBP being relatively more stable.