Tuning of intramolecular charge transfer properties and charge distributions in ferrocene-appended catechol derivatives by chemical substitution

摘要

In this study, we report intramolecular charge transfer (ICT) properties and charge distributions in a series of FcC derivatives (FcC = 4-ferrocenylcatecholate where Fc = ferrocene and C = catecholate). This series consists of a previously reported complex FcV (4-ferrocenylveratrole) and newly synthesized complexes FcA (4-ferrocenylcatechol bis(acetate) and Pt((t)Bu(2)bpy)(FcC) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-dipyridyl). An electrochemical analysis of Pt((t)Bu(2)bpy)(FcC) using cyclic voltammetry revealed two well-defined, reversible waves which were assigned to the sequential oxidation of the Pt((t)Bu(2)bpy)(C) and Fc moieties. The potential splitting between the waves (524 mV) indicated that there was an electronic interaction between both moieties. ICT property and charge distribution of [Pt((t)Bu(2)bpy)(FcC)](center dot+) were rationalized by comparison with the [FcV](center dot+) and [FcA](center dot+) (4-ferrocenylcatechol bis(acetate)). DFT calculations and UV-vis-NIR spectroscopy revealed that [Pt((t)Bu(2)bpy)(FcC)](center dot+), [FcV](center dot+), and [FcA](center dot+) were ferrocenium (Fc(+))-centered rather than semiquinone ligand-centered and that these complexes exhibited ICT transition bands from the catechol-derivatized framework to the Fc(+) moiety in the near infrared (NIR) region. Both the electronic coupling parameter (H-AB) and delocalization parameter (alpha) increased in value as the electron- donating strength of the substituent groups in the catechol-derivatized framework increased (OCOCH3 ([FcA](center dot+)) < OCH3 ([FcV](center dot+)) < O- ([Pt((t)Bu(2)bpy)(FcC)](center dot+))). The electronic interactions between the organometallic center and the non-innocent framework were tuned by changing the substituents. The potential energy surfaces of the Fc(+) derivatives, obtained using two-state Marcus-Hush theory, can be modulated by changing the energy level of the molecular orbitals of the appended catechol-derivatized moieties.