Acid/Base Switching of the Tautomerism and Conformation of a Dioxoporphyrin for Integrated Binary Subtraction

Abstract

Compared with most of the reported logic devices based on the supramolecular approach, systems based on individual molecules can avoid challenging construction requirements. Herein, a novel dioxoporphyrin DPH22 was synthesized and two of its tautomers were characterized by single-crystal X-ray diffraction studies. Compound DPH22 exhibits multichannel controllable stepwise tautomerization, protonation, and deprotonation processes through interactions with H(+) and F(-) ions. By using the addition of H(+) and F(-) ions as inputs and UV/Vis absorption values at λ=412, 510, 562, and 603 nm as outputs, the controlled tautomerism of DPH22 has been successfully used for the construction of an integrated molecular level half-subtractor and comparator. In addition, this acid/base-switched tautomerism is reversible, thus endowing the system with ease of reset and recycling; consequently, there is no need to modulate complicated intermolecular interactions and electron-/charge-transfer processes.

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

“…By utilizing the reactivity of 5,15‐PQs, which is typical to that of quinones, further transformations of PQs were accomplished . Metal complexes of 5,15‐PQs can be also be obtained similar to that of porphyrins . Very recently, we systematically studied the structure and physical properties of the divalent metal complexes of 5,15‐PQ .…”

Methodologies in Spectral Tuning of DSSC Chromophores through Rational Design and Chemical-Structure Engineering

“…The donor moiety of the reference parent PZn-EDOT dye, i.e., Zn-tetraphenylporphyrin, is depicted in Figure 9a. It is a widely utilized supramolecular chromophore building block [133]. The strong visible light absorption bands of Zinc-porphyrin derivatives are a result of π-π* transitions from the closely spaced HOMO and LUMO frontier valence orbital manifold [132,134].…”

Metal Complexes of 5,15‐Porphyrinquinones: Systematic Study of Crystal Structure, Electronic Structure, and Lewis Acidity

“…Like porphyrins, PQs can bind the metal ion to their center. In fact, Mg II , Mn III , Fe III , Ni II , Zn II ,, and Tl III[3] complexes have been reported to date. Although these metal complexes are also expected to have characteristics typical of quinone‐metal complexes, the properties of those complexes have not been adequately explored except for Fe III , Ni II ,, and Zn II[9–12] complexes, or the complexes with analogous ligands , .…”