Effect of Fluorine Substitution on Absorption and Emission Properties of Figure-eight-shaped [5]Helicene Dimer: A Computational Study at RI-MP2/RI-ADC(2) Level.

Chirality is a very important characteristic of optically active molecules and polyaromatics with helical structures, and plays a vital role in various applications in material science. In the present work, we show the effects of fluorine substitution at various positions in a figure-8-shaped [5]helicene dimer on the ground and excited state g-factors. Calculations for the ground and excited states are performed at the MP2 and ADC(2) levels of theory, respectively. The results reveal that fluorination has a large effect on the excited state structures. The values of the excited state dissymmetry factors for the molecules with fluorinations at both ends of the figure-8 systems are smaller than that of the parent system. On the other hand, fluorinations only in the stacked-phenyl region results in an increase in the value of g cpl ${\left| {g_{{\rm{cpl}}} } \right|}$ . The perfluorinated system shows the smallest g cpl ${\left| {g_{{\rm{cpl}}} } \right|}$ .

Effect of Terminal Fluorination on Chiroptical Properties of Carbo[5-8]helicenes: A Systematic Computational Study at the RI-ADC(2) Level.

In this article, effects of di-, tetra-, and octafluorination on the structural and chiroptical properties of carbo[5-8]helicenes are reported. Three fluorinated derivatives are designed from each parent carbohelicene by substituting either one, two, or four hydrogens at each terminal ring with fluorine atoms. Excited states properties such as UV-vis and CD spectra of all the six fluorinated carbohelicenes are computed at the ADC(2)/def2-TZVP level, and the results are compared against the results of their respective parent carbohelicene. In addition, CPL properties are also computed at the same level of theory. In the case of carbo[5]helicene (5H), gCPL decreases with an increase in the degree of fluorination. A similar observation is made in carbo[6]helicene (6H) too, although the value for tetrafluorinated 6H is slightly larger than for difluorinated 6H. Di- and tetrafluorination in carbo[7]helicene (7H), and all types of considered fluorination in carbo[8]helicene (8H) produce improved gCPL results. Results for fluorescence rate constants are also shown. Results are analyzed in terms of the transition dipole moment vectors and the angles between those.

Effects of Heterocyclic Ring Fusion and Chain Elongation on Chiroptical Properties of Polyaza[9]helicene: A Computational Study.

In the present work, the effect of lateral and helical extensions on the physical and chiroptical properties of azahelicenes is reported. Starting with the experimentally reported polyaza[9]helicene (9Ha), three derivatives, two with laterally fused electron-withdrawing rings and the third with larger helical length, are designed. For the excited-state properties such as UV-vis and CD spectra, performances of different DFT functionals are evaluated by comparing the energies and characters of the excited states against the ADC(2) results. CPL properties are calculated at DFT level. Among the three designed systems, pyrazine-based 9HaP shows an improved gCPL value compared to that for parent 9Ha. However, quinoxaline-based 9HaQ is found to be the worst CPL emitter with the lowest dissymmetry factor. The helically extended derivative, 11Ha, shows good CPL results, but gCPL remains smaller than that for the parent system. The CPL results are analyzed in terms of electric dipole transition moment (EDTM) and magnetic dipole transition moment (MDTM) vectors, and angles between these two vectors.

Assessing the Performance of DFT Functionals for Excited-State Properties of Pyridine-Thiophene Oligomers.

In this article, we have examined the accuracy of various density functional theory (DFT) functionals to reproduce the absorption and CD spectra of pyridine-thiophene oligomers. The performance of different levels of approximations in DFT functionals is discussed with reference to the ADC(2) results. Starting from a linear system, like monomer, calculations are carried out at ADC(2) and DFT levels till a helical system, like pentamer, is formed. For vertical excitation energies, results obtained with functionals, like CAM-B3LYP, ωB97XD, and M06-2X, are closer to the ADC(2) results. However, analysis of excited-state properties shows that the state ordering patterns or results regarding natural transition orbitals from these DFT functionals sometimes differ from the ADC(2) results. Global hybrid functionals like B3LYP and PBE0 produce excitation energies which are far away from the ADC(2) benchmark results. Similarly, pure functionals and their long-range corrected versions produce either redshifted or blueshifted energies. For the CD spectra, the above three mentioned functionals, CAM-B3LYP, ωB97XD, and M06-2X, again produce spectra closer to the benchmark spectra.