Design a better metalloporphyrin semiconductor: A theoretical studies on the effect of substituents and central ions

Abstract

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Puwere chosen as the central metal to see the effect of the elements on the nature of the group and the same period and reviewed the effect of substituent groups pull and push the electrons to the electronic properties of complex metalloporphyrin. The DFT/B3LYP/LANL2DZ and TD-DFT calculation were used to generate the optimized structure of, electronic and photophysical properties. The parameter is an Eg complex compound, DOS, and electronic absorption spectra. The calculations showed electron donating complexes tend to be better as a semiconductor because it lowers Eg complex compounds metalloporphyrin, NH2 group gave the smallest Eg compared to other groups.

Insights into the new cadmium(II) metalloporphyrin: Synthesis, X-ray crystal structure, Hirshfeld surface analysis, photophysical and cyclic voltammetry characterization of the (morpholine){(meso-tetra(para-chloro-phenyl)porphyrinato}cadmium(II)

“…The optical band gap energy (E g ) refers to the energy difference between the HOMO and the LUMO orbitales of the porphyrin species can be calculated from the UV-visible spectrum using the Tauc plot method [42]. The E g values in CH 2 Cl 2 solution are 1.960 and 1.903 eV for [Cd(TClPP)] and [Cd(TClPP)(morph)] respectively, indicating that the gap energy of the metallized species are higher than that obtained for H 2 TClPP free base (1.820 eV)(Table S2) suggesting that the Cd-meso-porphyrin display interesting organic semiconducting properties[43].…”

Molecular and Electronic Structure of Some Symmetrically meso-Substituted Hg(II)-Porphyrin Complexes

“…Previous study [9] showed that electron withdrawing group tend decrease the orbitals energy, but increase the gap. This effect is due to the effect of the electron density shift on the stability of the orbital is bigger on the occupied orbital than the virtual orbitals, thus decrease the orbital energy, but increase the gap between the orbitals.…”

“…Metalloporphyrin complexes performance as semiconducting materials is determined by the central ion of the complexes and the functional group that is substituted on the porphyrin ring [5,9]. We have previously discussed how those factors help us to design a better metalloporphyrin semiconductor by looking into the electronic structures of some meso-substituted M(II)-porphyrin (M = Pt, Cd, Hg) [9].…”

“…We have previously discussed how those factors help us to design a better metalloporphyrin semiconductor by looking into the electronic structures of some meso-substituted M(II)-porphyrin (M = Pt, Cd, Hg) [9]. In this paper we will further discussed the both electronic and molecular structure and properties of some meso-substituted Hg(II)-porphyrin.…”

“…On the other side, porphyrin and its derivatives were also known for their unique photoreactivity [1,2] and narrow band gap for semiconductor applications. Some of porphyrin derivatives in the form of metalloporphyrin complexes has been proven to have the properties of a semiconductor materials such as Pt(II)-porphyrin, Fe(II)-porphyrin, Mg(II)-porphyrin and zinc group-porphyrin complexes [3][4][5][6][7][8].Metalloporphyrin complexes performance as semiconducting materials is determined by the central ion of the complexes and the functional group that is substituted on the porphyrin ring [5,9]. We have previously discussed how those factors help us to design a better metalloporphyrin semiconductor by looking into the electronic structures of some meso-substituted M(II)-porphyrin (M = Pt, Cd, Hg) [9].…”