A new chiral perylene monoanhydride monoimide (1) with a sterically hindered chiral amine was successfully synthesized for further selective functionalization at terminal positions. At the same time, the chiral perylene diimide (2) with the same amine has been synthesized. The synthesized products were characterized using the data from NMR, IR, MS, UV-vis, DSC, TGA, elemental analysis and cyclic and square wave voltammetry. Compound 2 shows an excellent solubility of 200 mg mL(-1) in chloroform. The band gap energy (Eg), LUMO and HOMO energy values were 2.28, -3.77 and -6.05 eV for 2, respectively in chloroform. In solid state, the band gap energy (Eg), LUMO and HOMO energy values were 1.96, -4.22 and -6.18 eV for 1 and 1.92, -4.13 and -6.05 eV for 2, respectively. Whereas 1 (solid state: -0.58 and -0.69 V vs. ferrocene/ferrocenium couple) and 2 (in chloroform: -1.03 and -1.22 V vs. ferrocene/ferrocenium couple) show two reversible reduction steps, 2 exhibits only one reversible wave (solid state: -0.67 V vs. ferrocene/ferrocenium couple). The diffusion coefficients were determined as 1.91 x 10(-7) and 8.47 x 10(-7) cm2 s(-1) for 1 and 2 in solid state, respectively, and 1.27 x 10(-5) cm2 s(-1) for 2 in solution. The solid state emission ability of the chiral products ( is much more emissive than ) remains a challenge for photonic, electronic and sensor applications. 1 and 2 showed high thermal stability. Efficient prevention of intermolecular pi-pi contacts of fluorophores results in an excellent fluorescence emission in solid state and solubility for 2.

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Dehydrotropylium-Co(2)(CO)(6) ion (2) has been generated by the Lewis acid mediated ionization of alcohol (3); it is attacked by relatively strong nucleophiles (N>1), but undergoes a radical homocoupling in the presence of weak nucleophiles (N<1).

Dehydrotropylium-Co 2 (CO) 6 ion, 1, has been generated by the action of HBF 4 or BF 3 ·OEt 2 on the corresponding cycloheptadienynol complex 7, which in turn has been prepared in four steps from a known diacetoxycycloheptenyne complex. The reaction of 7 via 1 with several nucleophiles results in substitution reactions with reactive nucleophiles (N > 1) under normal conditions, and a radical dimerization reaction in the presence of less reactive nucleophiles. Competitive reactions of 7 with an acyclic trienynol complex, 12, shows no preference for generation of 1 over acyclic cation 13. DFT studies on 1, specifically evaluation of its HOMA value (+0.95), homodesmotic reaction based stabilization energy (ca. 2.8 kcal/mol) and NICS(1) value (-2.9), taken together with the experimental studies suggest that 1 is weakly aromatic.

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