Ethylene‐Bridged Tetradentate Bis(amidines): Supramolecular Assemblies through Hydrogen Bonding and Photoluminescence upon Deprotonation
Alvaro Calderón‐Díaz, Janet Arras, Ethan T. Miller, Nattamai Bhuvanesh, Colin D. McMillen, Michael Stollenz
Abstract
Sterically crowded tetradentate bis(amidines) encapsulate their N–H functionalities or unveil them to undergo inter‐ and intramolecular hydrogen bonding both in solid state and solution, depending on a subtle interplay between the amidine backbone substituents. X‐ray crystallography reveals for four distinct ZZ ( syn/syn ) and EE ( syn/syn ) bis(amidines) that bulky terminal N ‐Mes groups in combination with N 2 C‐ t Bu or N 2 C‐Ph substituents result in steric protection of the N–H moieties, whereas less crowded terminal p ‐ t Bu(C 6 H 4 ) groups either show encapsulation ( N 2 C‐ t Bu) or hydrogen bonding ( N 2 C‐Ph), the latter resulting in a bis(amidine) dimer formed by inter‐ and intramolecular hydrogen bonds. Moreover, a supramolecular solvent adduct consisting of one bis(amidine) and four ethanol molecules is presented. DFT calculations show that both the dimerization and formation of the solvent adduct is associated with a significant energy gain (dimerization: ΔE = –27.7 kcal/mol; formation of ethanol adduct: ΔE = –64.3 kcal/mol). The corresponding four Li bis(amidinates) are weakly blue to green‐emissive in THF solution. Overall, a new series of highly flexible bis(amidines) has been examined.