An Electropolymerized Crystalline Film Incorporating Axially-Bound Metalloporphycenes: Remarkable Reversibility, Reproducibility, and Coloration Efficiency of Ruthenium(II/III)-Based Electrochromism

Abstract

Oxidative electropolymeization of an axially bound, bithiophene-pyridine complex of ruthenium(III)-porphycene [Ru(TPrPc) (btp)2]PF6 (1) gives a submicrometer-thick, polymeric film on an ITO electrode with a crystalline morphology. The polymeric film, the first example of axially linked multimetalloporphycene coordination arrays, exhibits highly stable and reproducible electrochromic response with high electrochromic efficiency upon electrochemical control over the metal-centered electron transfer process (Ru(II)/Ru(III)).

Reversible Electropolymerization of Nickel Complexes Based on Redox‐Mediated Ligand Exchange

“…The CV profile of the deposited polymer film in the presence of free Br − demonstrates a redox couple at ∼ −0.7 eV with the peak separation Δ E p highly dependent on the scan rate (Figure S83). This behavior has been previously observed for electrodeposited metallopolymers and it is indicative of a diffusion‐controlled redox event associated with counterion (Br − ) mobility across the polymer film for charge neutralization through binding …”

Symmetry Reduction of Porphycenes with Finely Tuned Optical and Electronic Properties through Oxidative Cyclization of E/Z‐Mixed Dipyrroethenes

“…Next, the oxidative coupling reaction of AB-dipyrroethenes as precursors was performed to obtain ABAB-a nd ABBA-porphycenes.T he oxidative coupling reaction of 6 in the presence of p-TSAa st he acid catalyst, followed by oxidation with chloranil, gave unsymmetric porphycene 12 in 30 %y ield, with no product 13 formed. The substituent groups affected the precursor reactivity.T he oxidative coupling reaction of 7 in the presence of p-TSA, followed by oxidation with chloranil,a fforded unsymmetric porphycenes 14 and 15.H owever,t he separation of 14 and 15 failed owing to their similarp olarity and solubility.N ewly obtained symmetric porphycene 18,u nsymmetric AABB-porphycenes 8, 9,a nd 10,a nd ABAB-porphycene 12 were characterized by HRMS, 1 HNMR, 13 CNMR, 19 FNMR, and IR spectroscopy,i na ddition to X-ray crystallography (Figures S1-S32, S39-S40, and Ta bles S1-S5 in the Supporting Information). Newly obtained unsymmetric porphycenes 14 and 15 were characterized as am ixture by HRMS, 1 HNMR, 13 CNMR, 19 FNMR, and IR spectroscopy.T his represents the first report of the cross oxidative coupling of different dipyrroethenes to produce unsymmetric porphycenes ( Figure 1c).…”

“…Elemental analysis was performed at the Service Center of Elementary Analy-sis of Organic Compounds at Kyushu University. 1 HNMR and 13 CNMR spectra were recorded by using aB ruker Avance5 00 NMR spectrometer. 19 FNMR spectra were recorded by using aJ EOL JNM-ECZ400 NMR spectrometer.C hemical shifts were referenced against tetramethylsilane or the residual solvent peak as an internal standard.…”

Gram-scale synthesis of porphycenes through acid-catalyzed oxidative macrocyclizations of E/Z-mixed 5,6-diaryldipyrroethenes

“…13,14 Various porphycenes with meso-and b-substituents and their metal complexes have been reported to have tunable functionalities, crystallinities and solubilities. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] However, the main obstacle to the widespread application of porphycenes is the lack of efficient and economical methods for their production. Therefore, porphycene chemistry has advanced more slowly than that of the parent isomer porphyrin.…”