## 1 Introduction  
Due to their well-established enantioselective properties, inherently chiral linear or cyclic polyheterocycles are used as enantiodiscriminative chiral electrode surfaces [1, 2]. The chirality of these materials is not due to the presence of one or more stereogenic centers, but derives from a tailored torsion of the whole main molecular scaffold with rotational barriers too high to be overcome at room temperature. The molecular architecture is such that the stereogenic and the electroactive elements coincide [3]. The production of the enantiomers of chiral synthons with \(C_{2}\) symmetry and endowed with thiophene pendants involves a semipreparative resolution step based on enantioselective high-performance liquid chromatography (HPLC) on a chiral stationary phase (CSP) and successive oligomerization by oxidation of the collected enantiopure forms [4]. In particular, thiophene \(\alpha\)-positions involved in the oxidative coupling are homotopic and the products of oxidation maintain a complete reigeregularity. The homochiral oligomer products have the same (\(R\)) or (\(S\)) absolute configuration as the starting enantiomer and usually are formed from two to four structural units. When applied as chiral electrode surfaces in electrochemistry experiments, the inherently chiral oligothiophenes have been shown to produce impressive peak potential differences for the enantiomers of chiral probes that are reversed when the absolute configuration of the selector is changed [2, 3]. At a microscopic level, chromatographic enantioseparation of the atropisomeric monomers can be achieved when the resolvable enantiomers exploit enantiospecific differences in the interaction with the active sites of the selector used in the CSP [4; 5]. Nevertheless, it is noteworthy that the chiral recognition on a given CSP is a dynamic process (i.e., the adsorption of enantiomers onto CSP is a distribution equilibrium between two phases) and, even if thermodynamically favored, it can be hindered or prevented by the onset of competitive processes and equilibria involving the enantiomers. In other words, when a secondary competitive process involving the enantiomers occurs on the time scale required to perform the desired enantiodiscrimination, this latter process could be severely disturbed, or even compromised. Enantionerization of stereolabile enantiomers that invert their absolute configuration on the separation time scale is a well-known dynamic on-column process [6]. The peak splitting and/or deformation of peak profiles can also originate from the slow mass transfer, slow equilibration of analytes between stationary and mobile phase, insufficient stationary sites to adsorb analytes (due to overloading), fast self-aggregation, and eluent mismatches [7; 8; 9]. In this work, we report on the synthesis of a new chiral monomer for inherently chiral oligothiophenes, namely the compound 2,2'-bis(2,2',5',2',-terthiophen-5-yl)-3,3'-bithianaphthene (abbreviated as **BT2-T6**, Figure 1), and its semipreparative HPLC enantioseparation. **BT2-T6** belongs to the class of atropisomeric C\({}_{2}\) symmetric thiophene-based electroactive monomers whose progenitor is **BT2-T4**[3; 10], featuring the same atropisomeric core functionalized in 3 and 3' positions with 2,2-bithiophene groups and successfully resolved into antipodes by enantioselective HPLC analysis [11]. The key feature of **BT2-T4** relies on the fact that the chemical [12] or electrochemical oxidation of its enantiomers produces inherently chiral films showing outstanding enantiodiscrimination ability, both in chiral voltammetry [13; 14; 15] where the antipodes of probes, differing in their functional groups and stereogenic elements, are discriminated through cyclovoltammetry on the basis of the difference in their oxidative potentials.