Ferrocene-Containing Pseudorotaxanes in Crystals: Aromatic Interactions with Hammett Correlation

Yuji Suzaki; Tomoko Abe; Asami Takei; Yugo Fukuchi; Take-Aki Koizumi; Kohtaro Osakada; Masaki Horie

doi:10.3390/molecules27051745

Ferrocene-Containing Pseudorotaxanes in Crystals: Aromatic Interactions with Hammett Correlation

Molecules. 2022 Mar 7;27(5):1745. doi: 10.3390/molecules27051745.

Authors

Yuji Suzaki¹, Tomoko Abe¹, Asami Takei¹, Yugo Fukuchi¹, Take-Aki Koizumi², Kohtaro Osakada^{1

3}, Masaki Horie⁴

Affiliations

¹ Laboratory for Chemistry and Life Science, Tokyo Institute of Technology, 4259 Nagatsuta, Yokohama 226-8503, Japan.
² Advanced Instrumental Analysis Center, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi 437-8555, Shizuoka, Japan.
³ National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Ibaraki, Japan.
⁴ Department of Chemical Engineering, National Tsing-Hua University, 101, Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan.

Abstract

Single crystals of pseudorotaxanes, [(FcCH₂NH₂CH₂Ar)(DB24C8)][PF₆] (DB24C8 = dibenzo[24]crown-8, Fc = Fe(C₅H₄)(C₅H₅), Ar = -C₆H₃-3,4-Cl₂, -C₆H₃-3,4-F₂, -C₆H₄-4-F, -C₆H₄-4-Cl, -C₆H₄-4-Br, -C₆H₃-3-F-4-Me, -C₆H₄-4-I) and [(FcCH₂NH₂CH₂C₆H₄-4-Me)(DB24C8)][Ni(dmit)₂] (dmit = 1,3-dithiole-2,4,5-dithiolate), were obtained from solutions containing DB24C8 and ferrocenylmethyl(arylmethyl)ammonium. X-ray crystallographic analyses of the pseudorotaxanes revealed that the aryl ring of the axle moiety and the catechol ring of the macrocyclic component were at close centroid distances and parallel or tilted orientation. The structures with parallel aromatic rings showed correlation of the distances between the centroids to Hammett substituent constants of the aryl groups.

Keywords: Hammett constants; aromatic interaction; crystal structure; pseudorotaxane.