Mechanochemical Preparation of Dipyridyl-Naphthalenediimide Cocrystals: Relative Role of Halogen-Bond and π–π Interactions

Abstract

Naphthalenediimide derivates are a class of π-conjugated molecules largely investigated in the literature and used as building blocks for metal–organic frameworks or coformers for hydrogen-bond-based cocrystals. However, their tendency to establish halogen-bond interactions remains unexplored. By using a crystalline engineering approach, we report here four new cocrystals with N , N ′-di(4-pyrydyl)-naphthalene-1,4,5,8-tetracarboxidiimide and diiodo-substituted coformers, easily obtained via a mechanochemical protocol. Cocrystals were characterized via NMR, electron ionization mass spectrometry, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Crystallographic structures were then finely examined and correlated with energy framework calculations to understand the relative contribution of halogen-bond and π–π interactions toward framework stabilization.

On the Mechanism of Cocrystal Mechanochemical Reaction via Low Melting Eutectic: A Time-Resolved In Situ Monitoring Investigation

“…Cocrystals are typically synthesized in bulk via mechanochemistry; ,− however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood . Despite their evident utility, this lack of comprehension de facto inhibits the outbreak of cocrystals that remain confined within the boundaries of the pharmaceutical industry, − with the exception of a few examples. ,,− …”

Carbon-atom hybridization tunes the halogen-bond strength in the series of DABCO·C2H2n I2 (n = 0–2) cocrystals

“…3). However, these doubts contrast with the recent reports on an NÁ Á ÁI HaB-assisted cocrystal of DABCO with CHI 3 (Adeniyi et al, 2022), 1,3-diiodobicyclo[1.1.1]pentane and 1,3-bis(4-iodophenyl)bicyclo[1.1.1]pentane (Grover et al, 2021), iodobenzene with quinuclidine (Otte et al, 2021), and dipyridyl-naphthalenediimide with 1,4-diiodobenzene and 4,4 0 -diiododiphenyl (Mazzeo et al, 2021).…”

Accurate extrinsic and intrinsic peak broadening modelling for time-resolved in situ ball milling reactions via synchrotron powder X-ray diffraction

“…The ability to drive chemical transformation by means of mechanical force has been recently rediscovered as an attractive and cost-effective tool [1][2][3][4] for the synthesis of organic, [5][6][7][8][9][10] metal-organic [11][12][13][14][15][16] and inorganic compounds and materials. [17][18][19][20] Many traditional solution-based chemical reactions can be performed via mechanochemistry with no (or minimal) use of solvent.…”