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. 2018 May 16;9(1):1957.
doi: 10.1038/s41467-018-04246-0.

Hollow organic capsules assemble into cellular semiconductors

Boyuan Zhang  1 , Raúl Hernández Sánchez  1   2 , Yu Zhong  1 , Melissa Ball  1 , Maxwell W Terban  3 , Daniel Paley  2 , Simon J L Billinge  3   4 , Fay Ng  5 , Michael L Steigerwald  1 , Colin Nuckolls  6   7
Affiliations

Hollow organic capsules assemble into cellular semiconductors

Boyuan Zhang et al. Nat Commun. .

Abstract

Self-assembly of electroactive molecules is a promising route to new types of functional semiconductors. Here we report a capsule-shaped molecule that assembles itself into a cellular semiconducting material. The interior space of the capsule with a volume of ~415 Å3 is a nanoenvironment that can accommodate a guest. To self-assemble these capsules into electronic materials, we functionalize the thiophene rings with bromines, which encode self-assembly into two-dimensional layers held together through halogen bonding interactions. In the solid state and in films, these two-dimensional layers assemble into the three-dimensional crystalline structure. This hollow material is able to form the active layer in field effect transistor devices. We find that the current of these devices has strong response to the guest's interaction within the hollow spaces in the film. These devices are remarkable in their ability to distinguish, through their electrical response, between small differences in the guest.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1
Fig. 1
Structures of cellular semiconductors. a Trimer 1; and b 1-Br12. Van der Waals Surface of 1-Br12 seen from the side (c), and top (f). In the sequence c-e and f–h the molecule is trimmed down to expose its cavity or capsule
Fig. 2
Fig. 2
Molecular structure from SCXRD of 1-Br12. a Side and b top view of (SSS)-1-Br12. C, N, O, S, and Br atoms are colored in gray, blue, red, yellow, and brown, respectively. Hydrogen atoms have been removed to clarify the view. The alkyl chains on the imide are refined to only nine of the eleven carbon atoms due to disorder (see Supplementary Methods)
Fig. 3
Fig. 3
Structural packing of 1-Br12. a View of the honeycomb structure in the ab plane for 1-Br12. The capsule and i corresponds to the internal cavity of 1-Br12 and the cavity formed by the packing of 1-Br12, respectively. The remaining sulfur atoms are colored in yellow to provide a marker to identify the macrocycle cavities. See bottom left cartoon. Highlighted in green are the imide side chains (some of the sidechains have been removed to clarify the view of the cavity). In red are the thiophene rings likely involved in holding the macrocycles together. b Surface map of the void space in the ab plane of 1-Br12. c Two molecules of 1-Br12 where the thiophene-to-thiophene interaction is highlighted as an inset. Bottom left cartoon represents this interaction. d View of the packing of 1-Br12. As shown, the vertical stacking follows the c axis. The alkyl sidechains of the imide are shown in green. Hydrogen atoms have been removed from all structures to clarify the view
Fig. 4
Fig. 4
Electron transport for cellular films. a Transfer characteristics of OFET device for 1-Br12. b Device cycling response under vacuum (red circles) and N2 atmosphere (blue triangles). c Normalized behavior of the device response under vacuum (step 1), N2 (step 2), and different analytes atmosphere (step 3: n-hexane, 3-hexyne and 1-hexyne). Error bars represent the standard error obtained in three measurements
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