Homoleptic complexes of isocyano- and diisocyanobiazulenes with a 12-electron, ligand-based redox capacity.

Oligo- and polyazulenes are attractive π-conjugated building blocks in designing advanced functional materials. Herein, we demonstrate that anchoring one or both isocyanide termini of the redox non-innocent 2,2'-diisocyano-6,6'-biazulenic π-linker (1) to the redox-active [Cr(CO) 5 ] moiety provided a convenient intramolecular redox reference for unambiguously establishing that the 6,6'-biazulenic scaffold undergoes a reversible one-step 2 e - reduction governed by reduction potential compression/inversion. Treatment of bis(η 6 -naphthalene)chromium(0) with six equiv. of 2-isocyano-1,1',3,3'-tetraethoxycarbonyl-6,6'-biazulene (6) or [(OC) 5 Cr(η 1 -2,2'-diisocyano-1,1',3,3'-tetraethoxycarbonyl-6,6'-biazulene)] (11) afforded homoleptic Cr(0) complexes 13 and 14 with a 12 e - (per molecule) ligand-based reduction capacity at mild E 1/2 of -1.29 V and -1.15 V vs. Cp 2 Fe 0/+ , respectively. The overall reversible redox capacity varies from 15 e - for the mononuclear complex 13 to 21 e - for the heptanuclear complex 14. The latter "nanocomplex" has a diameter of ca. 5 nm and features seven Cr(0) centers interlinked with six 2,2'-diisocyano-6,6'-biazulenic bridges. The X-ray structure of [(OC) 5 Cr(2-isocyano-1,1',3,3'-tetraethoxycarbonyl-6,6'-biazulene)] (7) indicated a 43.5° interplanar angle between the two azulenic moieties. Self-assembly of 11 on a Au(111) substrate afforded an organometallic monolayer film of 11 featuring approximately upright orientation of the 2,2'-diisocyano-6,6'-biazulenic linkers, as evidenced by ellipsometric measurements and the RAIR signature of the C 4v -symmetric [(-NC)Cr(CO) 5 ] infrared reporter within 11. Remarkably, comparing the FTIR spectrum of 11 in solution with the RAIR spectrum of 11 adsorbed on Au(111) suggested electronic coupling at a ca. 2 nm distance between the Cr(0) and Au atoms linked by the 2,2'-diisocyano-6,6'-biazulene bridge.