Naslov
Halogen-bonding deeper into the periodic table: molecular cocrystals with phosphorus, arsenic and antimony acceptors

Autori
Lisac, Katarina ; Topić, Filip ; Arhangelskis, Mihails ; Cepić, Sara ; Julien, Patrick A. ; Nickels, Christopher W. ; Morris, Andrew J. ; Friščić, Tomislav ; Cinčić, Dominik

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
II. simpozij supramolekulske kemije - knjiga sažetaka / Frkanec, Leo ; Namjesnik, Danijel ; Tomišić, Vladislav - Zagreb : Institut Ruđer Bošković, 2018, 14-14

ISBN
978-953-7941-26-0

Skup
2. simpozij supramolekulske kemije

Mjesto i datum
Zagreb, Hrvatska, 12.12.2018

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Podatak o recenziji nije dostupan

Ključne riječi
halogen-bonded cocrystals, phosphorus, arsenic and antimony acceptors, experimental and theoretical study

Sažetak
Halogen bonding has emerged as a viable alternative to hydrogen bonding in crystal engineering and is currently the only class of sigma-hole interactions, commonly used in the rational assembly of cocrystals, liquid crystals and other types of functional materials.1 The formation of halogen bonds is a central concept of materials design, which hinges on using small compact atoms of the 2nd period, notably nitrogen and oxygen, as acceptors. Heavier atoms are much less prominent in that context, and mostly limited to sulphur.1-3 In this work, we report the first experimental observation and theoretical study of halogen bonds to phosphorus, arsenic and antimony in the solid state. Combining 1, 3, 5- triiodotrifluorobenzene (tftib) with triphenylphosphine (PPh3), -arsine (AsPh3), and - stibine (SbPh3) provided the first examples of cocrystals based on I···P, I···As and I···Sb halogen bonds. Products were obtained by mechanochemical and solution-based synthesis and characterized by means of powder X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, FTIR-ATR spectroscopy and single crystal X-ray diffraction. Mechanochemical experiments for all cocrystals were followed in situ by Raman spectroscopy. Obtained cocrystal structures, combined with gas- phase and solid-state theoretical calculations, show that P, As and Sb can act as respectable XB acceptors in the solid state, forming contacts that are 11-12% shorter than the sums of van der Waals radii, with calculated dissociation energies between 12-17 kJ mol−1. To evaluate the I···P, I···As and I···Sb halogen bonds, as well as to explain the inability to synthesize cocrystals of BiPh3 and NPh3, we conducted a theoretical study of putative gas-phase complexes (tftib)(EPh3) [E = N, P, As, Sb, Bi] and of crystal structures of all three obtained cocrystals using periodic density functional theory. The presented work is a novel contribution not only to the field of halogen bonding, but also to supramolecular chemistry overall, as it introduces three new elements as components of halogen-bonded cocrystals and expands the supramolecular chemistry of arsenic and antimony. 1 G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimagi, G. Resnati and G. Terraneo, Chem. Rev. 2016, 116, 2478. 2 F. Topić, K. Rissanen, J. Am. Chem. Soc. 2016, 138, 6610 3 D. Cinčić, T. Friščić, W. Jones, CrystEngComm 2011, 13, 3224.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA