NIR-Absorbing Donor–Acceptor Based 1,1,4,4-Tetracyanobuta-1,3-Diene (TCBD)- and Cyclohexa-2,5-Diene-1,4-Ylidene-Expanded TCBD-Substituted Ferrocenyl Phenothiazines

Abstract

A series of unsymmetrical (D-A-D1, D1-π-D-A-D1, and D1-A1-D-A2-D1; A=acceptor, D=donor) and symmetrical (D1-A-D-A-D1) phenothiazines (4 b, 4 c, 4 c′, 5 b, 5 c, 5 d, 5 d′, 5 e, 5 e′, 5 f, and 5 f′) were designed and synthesized by a [2+2] cycloaddition–electrocyclic ring-opening reaction of ferrocenyl-substituted phenothiazines with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ). The photophysical, electrochemical, and computational studies show a strong charge-transfer (CT) interaction in the phenothiazine derivatives that can be tuned by varying the number of TCNE/TCNQ acceptors. Phenothiazines 4 b, 4 c, 4 c′, 5 b, 5 c, 5 d, 5 d′, 5 e, 5 e′, 5 f and 5 f′ show redshifted absorption in the λ=400 to 900 nm region, as a result of a low HOMO–LUMO gap, which is supported by TD-DFT calculations. The electrochemical study exhibits reduction waves at low potential due to strong 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and cyclohexa-2,5-diene-1,4-ylidene-expanded TCBD acceptors. The incorporation of cyclohexa-2,5-diene-1,4-ylidene-expanded TCBD stabilized the LUMO energy level to a greater extent than TCBD. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim