Assembling phenomena of calix[4]hydroquinone nanotube bundles by one-dimensional short hydrogen bonding and displaced pi-pi stacking.
Using the computer-aided molecular design approach, we recently reported the synthesis of calix[4]hydroquinone (CHQ) nanotube arrays self-assembled with infinitely long one-dimensional (1-D) short hydrogen bonds (H-bonds) and aromatic-aromatic interactions. Here, we assess various calculation methods employed for both the design of the CHQ nanotubes and the study of their assembly process. Our calculations include ab initio and density functional theories and first principles calculations using ultrasoft pseudopotential plane wave methods. The assembly phenomena predicted prior to the synthesis of the nanotubes and details of the refined structure and electronic properties obtained after the experimental characterization of the nanotube crystal are reported. For better characterization of intriguing 1-D short H-bonds and exemplary displaced pi-pi stacks, the X-ray structures have been further refined with samples grown in different solvent conditions. Since X-ray structures do not contain the positions of H atoms, it is necessary to analyze the system using quantum theoretical calculations. The competition between H-bonding and displaced pi-pi stacking in the assembling process has been clarified. The IR spectroscopic features and NMR chemical shifts of 1-D short H-bonds have been investigated both experimentally and theoretically. The dissection of the two most important interaction components leading to self-assembly processes would help design new functional materials and nanomaterials.
Kim
Kwang S
KS
National Creative Research Initiative Center for Superfunctional Materials and Department of Chemistry, Division of Molecular and Life Sciences, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang 790-784, Korea. kim@postech.ac.kr
Suh
Seung Bum
SB
Kim
Jong Chan
JC
Hong
Byung Hee
BH
Lee
Eun Cheol
EC
Yun
Sunggoo
S
Tarakeshwar
P
P
Lee
Jin Yong
JY
Kim
Yukyung
Y
Ihm
Hyejae
H
Kim
Heon Gon
HG
Lee
Jung Woo
JW
Kim
Jung Kyung
JK
Lee
Han Myoung
HM
Kim
Dongwook
D
Cui
Chunzhi
C
Youn
Suk Joo
SJ
Chung
Hae Yong
HY
Choi
Hyuck Soon
HS
Lee
Chi-Wan
CW
Cho
Seung Joo
SJ
Jeong
Sukmin
S
Cho
Jun-Hyung
JH
D047250:Calixarenes; D017076:Computer-Aided Design; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D006873:Hydroquinones / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D036103:Nanotechnology / Q000379:methods*; D011809:Quinones / Q000138:chemical synthesis / Q000737:chemistry
D006873:Hydroquinones; D011809:Quinones; C469855:calix(4)hydroquinone; D047250:Calixarenes