Efficient and tunable enhancement of NLO performance for indaceno-based donor moiety in A-π-D-π-D-π-A type first DSSC design by end-capped acceptors

Abstract

Using 2,2'-((4-heptyl-4,9,9-trihexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7diyl)bis(methanylylidene)bis(3-oxo-2,3-dihydro-1H-indene-1-yl-2-ylidene)dimalononitrile (IDIC) as a starting point, a series of non-fullerene acceptor (NFA) related dyes (IDIC-R1-IDIC-R9) are designed by varying the end capped fluorinated (1-oxo-1H-inden-3yl)propanedinitrile moieties (A1-A6). At the M06 level, DFT and TD-DFT based features, including the 6-31G(d,p) basis set, were created to investigate NLO responses to acceptor modification. For IDIC to IDIC-R a significant reduction of band gap (2.01 eV) was observed all the dyes (IDIC-R1-IDIC-R9) had further reduced band gaps to range between 0.11-2.42. Only IDIC-R3 had higher value that the IDIC-R, demonstrating smaller and bigger levels for and softness properties, and was linked to global reactivity data. Their first ionization potential ranged between the 2.65-7.21 eV to imply that the dyes have strong tendency to lose electrons.The λmax of the dyes ranged between 479-498 nm which were slightly redshifted from the IDIC (476 nm) and IDIC-R (479 nm). NBO analysis showed the S63LP→C61-C62π* with highest stabilization energy of 30.11 kcal/mol. Their electron injection analysis showed that these dyes can be a good anode material against the aluminum and gold electrodes with HIE values range of 6.87-11.49 eV. The intra electronic charge transferring (ICT) process and stability of the title dyes pounds were investigated using frontier molecular orbital (FMO) and natural bond orbital (NBO) research, respectively. For all produced dyes, IDIC-R8 has the highest linear polarizability, and second order hyperpolarizability (βtotal). All the suggested dyes demonstrated possible NLO properties due to their low charge transfer barriers. Scientists would be able to exploit these NLO properties to identify NLO materials for existing applications.

Molecular modeling of the structural, electronic, excited state dynamic, and the photovoltaic properties of the oligomers of n-corannulene (n = 1–4)

“…In general, negative LUMO energy levels suggest strong chemical activity of the structures, so E LUMO gives an approximation of electron affinity (A = -E LUMO ) [ [32] , [33] , [34] , [35] ] . Similarly, E HOMO can estimate the ionization potential (I = -E HOMO ).…”

“…Consequently, a remarkable 49.5 % decrease in the energy gap is observed in 4-Corannulene. Notably, the comparison between the energy of HOMO and LUMO frontier orbitals and the energy gap highlights the significant influence of the LUMO frontier orbital on this gap [ 34 , 35 ]. By reducing the energy gap in the molecule, the possibility of quantum tunneling arises, potentially enhancing the electrical conductivity of the examined structure.…”

Photovoltaic and Optical Characterization of Organic Heterocyclic 6,6′‐Dibromoindigotin Crystal Under Changing Solvent Polarity by DFT Analysis

“…Optical chromophores such as Donor-Acceptor (D-A) type molecules are widely used in optical switches due to their strong optical properties. [26] They are typically composed of an electron donor group and an electron acceptor group, which are linked by a conjugated bridge. [27] In addition to them, other crystalline materials such as perovskites [18] and quantum dots [28] are also being explored for use in solar cells.…”