A molecular glass compound comprises a vinyl ether adduct of an aromatic vinyl ether of formula C(R1)2═C(R2)—O-(L)n-Ar1, and a calix[4]arene, wherein R1 and R2 are each independently a single bond, H, C1-20 alkyl, C1-20 haloalkyl, C6-20 aryl, C6-20 haloaryl, C7-20 aralkyl, or C7-20 haloaralkyl, L is a C1-20 linking group, n is 0 or 1, and Ar1 is a halo-containing monocyclic, or substituted or unsubstituted polycyclic or fused polycyclic C6-20 aromatic-containing moiety, wherein R1 and R2 are connected to Ar1 when either or both of R1 and R2 is a single bond and n is 0. A photoresist, comprising the molecular glass compound, a solvent, and a photoacid generator, a coated substrate, comprising (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition over the one or more layers to be patterned, and a method of forming the molecular glass compound, are also disclosed.