G5 Doctoral dissertation (article)
Halogen bond in crystal engineering : structural studies on crystals with neutral ruthenium centered complexes and 1-(4-pyridyl)-4-thiopyridine zwitterion as halogen bond acceptors (2020)


Ding, Xin (2020). Halogen bond in crystal engineering : structural studies on crystals with neutral ruthenium centered complexes and 1-(4-pyridyl)-4-thiopyridine zwitterion as halogen bond acceptors. JYU dissertations, 323. Jyväskylä: Jyväskylän yliopisto. http://urn.fi/URN:ISBN:978-951-39-8420-5


JYU authors or editors


Publication details

All authors or editors: Ding, Xin

eISBN: 978-951-39-8420-5

Journal or series: JYU dissertations

eISSN: 2489-9003

Publication year: 2020

Number in series: 323

Number of pages in the book: 1 verkkoaineisto (59 sivua, 32 sivua useina numerointijaksoina, 16 numeroimatonta sivua)

Publisher: Jyväskylän yliopisto

Place of Publication: Jyväskylä

Publication country: Finland

Publication language: English

Persistent website address: http://urn.fi/URN:ISBN:978-951-39-8420-5

Open Access: Publication published in an open access channel


Abstract

This work focuses on using both ruthenium complexes and a newly synthesized organic zwitterion as halogen bond (XB) acceptors to construct a series of crystal structures and to investigate the selectivity of halogen bond. p-Diiodotetrafluorobenzene (p-DITFB) was used as the halogen bond donor to co-crystalize with [Ru(bpy)(CO)2X2] (X=Cl, Br, I), yielding a series of crystals 1-3. The strength of X…I in 1-3 follows the order of Ru-Cl>Ru-Br>Ru-I, indicating electrostatic nature of the XBs. Isomorphic [Ru(bpy)(CO)2Cl2]•p-DITFB (1) and [Ru(bpy)(CO)2Br2]•p-DITFB (2), with both halido ligands involved in XB, form zig-zag chains, which expand into 3D network with solvent accommodating voids. [Ru(bpy)(CO)2I2]•p-DITFB (3) forms linear chains with only one of the two iodo ligands involved in XB. The neighboring linear chains are further linked together via F…O interaction to form 3D networks. The XB preference for S over N in the sulfur coordinated thiocyanate ligand of [Ru(bpy)(CO)2(S-NCS)2] was studied with I2 as XB donor. The computational analysis results, which demonstrate no major energy differences between SCN…I and NCS…I system, suggest the pivotal role of packing effect. Moreover, because of the narrower energy gap between HOMO and LUMO in [Ru(bpy)(CO)2(S-NCS)2]•2I2 than in [Ru(bpy)(CO)2(S-NCS)2]•I2 (4), the singly interacting adduct (4) was the only experimentally obtained structure, regardless of the amount of I2 used. A new bidentate XB acceptor, 1-(4-pyridyl)-thiopyridine (PTP), incorporating both bidentate sp3-S and monodentate sp2-N, has been synthesized. Three crystals (5-7) were obtained from co-crystalizing the PTP with p-diiodobenzene (DIB), p-DITFB, and iodopentafluorobenzene (IPFB), respectively. The structure of 5-7 demonstrate the selectivity of XB between S and N as well. All the results from this study prove that XB is a viable tool in constructing extended metal networks with [Ru(bpy)(CO)2X2], and, however, indicate that all the other intermolecular interactions, along with XB, also exert unneglectable impact on the crystal formation.


Keywords: coordination complexes; aromatic compounds; halogens; crystals; chemical synthesis; chemical bonds

Free keywords: crystal engineering; halogen bond; electrostatic; selectivity


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Ministry reporting: Yes


Last updated on 2020-07-12 at 14:48