3,6‐Divinyl‐N‐arylcarbazoles‐bridged diruthenium complexes bearing two Ru(CO)Cl(PiPr3)2 moieties: Polyelectrochromism and electronic coupling

Abstract

A series of five 3,6‐divinyl‐N‐arylcarbazoles‐bridged diruthenium complexes with a general formula of [{Ru(CO)Cl(PiPr3)2}2(μ‐(CH=CH)2‐(N‐arylcarbazole)‐3,6); aryl = 4‐anisyl; [1a], 4‐tolyl; [1b], phenyl; [1c], 4‐(trifluoromethyl)phenyl; [1d], and 4‐nitrophenyl; [1e]] were successfully synthesized. These new square‐pyramidal bis(ruthenium‐vinyl)‐type complexes were characterized in their neutral state via classical NMR, UV/Vis, and IR spectroscopic techniques and in their three various accessible oxidized states via electrochemical techniques and ESR spectroscopy along with UV/Vis/NIR and IR spectroelectrochemistry as well as with DFT calculations. Our obtained results were compared with the closely related bis(ruthenium‐vinyl)‐appended N‐(4‐anisyl)diphenylamine TAARu2 counterpart of [1a]. Electrochemical studies on complexes [1a]–[1e] revealed three consecutive, chemically and electrochemically, well‐separated, reversible one‐electron oxidation processes at low and well‐accessible potentials. Their half‐wave potential separations ΔE½ between the individual redox waves and the derived comproportionation constants Kc1–Kc3 attribute to noteworthy stability of every oxidized intermediate state. The concert electrochemical and UV/Vis/NIR/IR spectro(electro)scopic results on these rotationally restricted N‐arylcarbazoles‐bridged bis(ruthenium‐alkenyl)‐type complexes [1a]–[1e] confirmed the relative weakness influence of altering the para‐substituent on the peripheral aryl ring. This is most probably due to the sizable torsion with nearly 55° between the co‐planarity of the carbazole heterocycle core and the peripheral N‐bound aryl ring. In their mixed‐valent (MV) radical states [1a]+–[1e]+, the observed pattern of two well‐separated Ru(C≡O) bands mirrors the uneven distribution of the uni‐positive charge over the two chemically equivalent bis(ruthenium‐vinyl) moieties as indicated by classical class II of Robin–Day classification of MV states.