Synthesis, photophysical and electronic properties of tetra-donor- or acceptor-substitutedortho-perylenes displaying four reversible oxidations or reductions

Abstract

Tetra-substitutedortho-perylenes bearing four strong Ar2N π-donors or Ar2B π-acceptors enable four reversible oxidations or four reductions.

Insights into the Optical Properties of Triarylboranes with Strongly Electron‐Accepting Bis(fluoromesityl)boryl Groups: when Theory Meets Experiment

“…A large number of air-stable conjugated three-coordinate organoboron compounds have been synthesized over the last few decades [1][2][3][4][5][6][7][8] for various applications, particularly in linear [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] and nonlinear [25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] optics, electro-optic devices, [40][41][42] anion sensors, [43,44] cell imaging, [45][46][47][48] etc. The boron center in these species possesses an empty p-orbital and can thus serve as a strong π-acceptor following photo-excitation, or as a readily reducible center.…”

Synthesis, Photophysical and Electronic Properties of Mono‐, Di‐, and Tri‐Amino‐Substituted Ortho‐Perylenes, and Comparison to the Tetra‐Substituted Derivative

“…The syntheseso ft he compounds (DPA)-Per, (DPA) 2 -Per and (DPA) 3 -Per are summarized in Scheme 1. We used the same startingp oint for the synthesis of the new derivatives as for our previouslyr eported [30] tetra-substituted ortho perylene (DPA) 4 -Per,w hich is the high yielding, regioselective Ir-catalyzed CÀHb orylation of perylene.I no rder to obtain the mono-, di-, and tri-borylated derivatives, the number of equiva-lents of B 2 pin 2 was reduced from 5t o1 .T hus, am ixture of Bpin-Per, (Bpin) 2 -Per, (Bpin) 3 -Per ands ome (Bpin) 4 -Per was obtained. The mono-a nd di-borylated products were successfully separated by column chromatography.T wo furtherr egioisomerso f(Bpin) 2 -Per are possible, namely 2,5-bis(Bpin)-perylenea nd 2,11-bis(Bin)-perylene.H owever,t hese two isomers could not be isolated, whereas 2,8-bis(Bpin)-perylene ((Bpin) 2 -Per)w as isolated successfully.F or the follow-up reactions, the tri-borylated perylene, in contrast, was used as amixture containing some residual di-borylatedp erylene.…”

“…Medium [30] the third and fourth oxidations of (DPA) 4 -Per are quite close to each other; therefore, we previously conducted af urther measurement using the weakly coordinating anion (WCA)-containing electrolyte [nBu 4 N][Al(OC(CF 3 ) 3 ) 4 ]t hat is known to separatec harged speciesbetter in electrochemical studies. Hence, four reversible oxidations at 0.04, 0.24, 0.41 and 0.51 Vw ith respect to Fc/Fc + were detected.…”

“…Hence, four reversible oxidations at 0.04, 0.24, 0.41 and 0.51 Vw ith respect to Fc/Fc + were detected. [30] Thus, we now have as eries of perylene derivatives which allows one to tune the electrochemical properties dependingo nt he requirements of ap articular application.…”

Electronically Driven Regioselective Iridium‐Catalyzed C−H Borylation of Donor‐π‐Acceptor Chromophores Containing Triarylboron Acceptors

“…The relevance of boron in these systems is due to the empty p z ‐orbital on boron that can act as an electron acceptor (A) in conjugated systems. Based on this, potential applications of three‐coordinate boron have been investigated, such as for linear and non‐linear optics, bioimaging, sensors, frustrated Lewis pairs (FLPs), and organic light‐emitting diodes (OLEDs) . The drawback of the employment of three‐coordinate boron in conjugated systems, however, is their inherent reactivity towards nucleophiles, such as water, due to the empty p z ‐orbital.…”