Efficient integration of layered transition metal dichalcogenides (LTMDs) into bulk manufacturing technologies (e.g. spray coating, inkjet printing, slot-dye coating, etc..) requires approaches that maintain 2D optoelectronic properties, as well as ensure compatibility with processing media and surrounding matrices. In particular, Group V LTMDs provide unique semi-metallic and opto-magnetic properties, but are hydrolytically unstable. Surface hybridization presents opportunities to address these challenges, by modulating interfacial properties while preventing hydrolysis-based decomposition. Herein, we show that basal surfaces of Redox Exfoliated Group V LTMDs can be hybridized utilizing lewis acid/base pair chemistry in anhydrous, aprotic solvents (CHCl<sub>3</sub>, THF, CH<sub>3</sub>CN), allowing for robust, stable colloidal dispersions. Amine, phosphine, and arsine moieties saturate frontier d-orbital occupancy via electron donation.  This increases the hydrolytic stability of Group V LTMDs, as well as transforms the native metallic state to semiconducting.  Furthermore, these hybridization reactions are stoichiometrically controlled and robust to omega functionality such as -ene, -yne, and aldehydes for further derivatization, creating new opportunities for development of multi-functional assemblies, coatings, and devices.

Basal surface functionalization of redox exfoliated group V LTMDs

ACS Spring 2022

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