Influence of phenyl-attached substituents on the vibrational and electronic spectra of meso-tetraphenylporphyrin: A DFT study

Chirogenesis in Zinc Porphyrins: Theoretical Evaluation of Electronic Transitions, Controlling Structural Factors and Axial Ligation

“…In the present work, the meso ‐position was chosen for peripheral substitutions, since it does not significantly distort the porphyrin plane,[ 100 , 101 ] that is an important aspect for our study, in contrast to the β ‐substituents. [ 67 , 102 , 103 , 104 , 105 , 106 ] Essentially, two substituents at the 5‐ and 15‐positions were chosen and classified to be either neutral (R=H, Ph), with electron‐donating (CH 3 , NMe 2 , OMe, Ph−Me‐ p , Ph−NMe 2 ‐ p , Ph−OMe‐ p , C≡C−Ph−NMe 2 ‐ p ), or electron‐withdrawing (CF 3 , NO 2 , CN, F, OC(O)H, Ph−CF 3 ‐ p , C≡C−Ph−NO 2 ‐ p ) groups.…”

“…It is of note that several functionalized Ph substituents were analyzed. Though these substituents usually do not have electron density in their frontier molecular orbitals resulting in a minor influence on the electronic structure,[ 59 , 69 , 71 , 101 , 103 , 107 ] they serve as secondary chromophores, the properties of which can easily be tuned by changing the functional groups at the Ph ring. Also, it should be noted that the meso ‐substituents cover only a part of the electronic perturbations.…”

Magnetic Circular Dichroism of Transition-Metal Complexes of Perfluorophenyl-N-Confused Porphyrins: Inverting Electronic Structure through a Proton

“…The electronic structure of normal porphyrins has been extensively studied, − but much work remains in the investigation of the electronic structures of isomers and analogues of porphyrins. Isomers of porphyrins include ring rearranged macrocycles, such as porphycene, while analogues of porphyrins are skeletal modified macrocycles such as expanded, contracted or ring modified systems. − Both types of macrocycles share many of the characteristics of normal porphyrin.…”

Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects

“…The substituent effects at the p -position of the meso -phenyl group are typically trivial in tetraphenylporphyrins because of the high rotation barrier and almost perpendicular orientation of the meso -phenyl groups. 88 In contrast, the optical properties of meso -aryl subporphyrins are significantly perturbed by the substituents. For example, 4-nitrophenyl-substituted subporphyrin 10 (ref.…”