Highly Efficient versus Null Electrochemical Enantioselective Recognition Controlled by Achiral Colinkers in Homochiral Metal-Organic Frameworks.

Chiral materials capable of electrochemical enantiomeric recognition are highly desirable for many applications, but it is still very challenging to achieve high recognition efficiency for lack of the knowledge of structure-property relationships. Here, we report the completely distinct enantiomeric recognition related to slightly different achiral colinkers in isomorphic homochiral metal-organic frameworks with the same chiral linker. Cu-TBPBe, for which the achiral colinker has two pyridyl rings connected by ─CH═CH─, shows excellent enantioselectivity and sensitivity for electrochemical recognition of l-tryptophan (Trp) with a detection limit of 3.16 nM. The l-to-d ratio of differential pulse voltammetric (DPV) currents reaches 53, which is much higher than the values (2-14) reported for previous electrochemical sensors. By contrast, Cu-TBPBa, in which the achiral colinker has -CH-CH- between pyridyl rings, is incapable of discrimination between l-Trp and d-Trp. Structural and spectral analyses suggest that the achiral conjugated colinker and the chiral moieties around it cooperate to produce a chiral pocket in favor of enantioselective adsorption through multiple hydrogen-bonding and π-π stacking interactions. The work demonstrated that Cu-TBPBe can be used to fabricate reliable electrochemical sensors for ultrasensitive quantification of Trp enantiomers in racemic mixtures and in complex biological systems such as urine. The work also highlights that an achiral coligand can be of vital importance in determining enantiomeric discrimination, opening up a new avenue for the design of chiral sensing materials.