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An important part of nursing care is the physiotherapist’s physical exercise recovery training (for instance, walking), which is aimed at restoring athletic ability, known as rehabilitation (rehab). In rehab, the big problem is that it is difficult to maintain motivation. Therapies using robots have been proposed, such as animalistic robots that have positive psychological, physiological, and social effects on the patient. These also have an important effect in reducing the on-site human workload. However, the problem with these robots is that they do not actually understand what emotions the user is currently feeling. Some studies have been successful in estimating a person’s emotions. As for non-cognitive approaches, there is an emotional estimation of non-verbal information. In this study, we focus on the characteristics of real-time sensing of emotion through heart rates – unconsciously evaluating what a person experiences – and applying it to select the appropriate turn of phrase by a voice-casting robot. We developed a robot to achieve this purpose. As a result, we were able to confirm the effectiveness of a real-time emotion-sensitive voice-casting robot that performs supportive actions significantly different from non-voice casting robots.

Although we have been developing a Virtual Grid (VG) system, where USB-PD-connected devices can alternatively provide and receive electrical power, we have not investigated the desirable power paths in a multiple-VG-Hub network. Our previous study shows that a power loss occurred inside the VG Hub. To minimize the total power loss, the number of used links needs to be minimized; the total power flow in the VG Hub network is minimized. In this paper, we have designed and implemented a cloud-based control system to execute the optimization with preceding local optimization. The experiment result has shown that the proposed hybrid type control algorithm can find the solution in 40% of the computational time on average compared with the algorithm that performs global optimization every time in the network where the solution can be found locally.

Chirality in two dimensions (2D) has attracted increasing attention with regard to interesting fundamental aspects as well as potential applications. This article reports several aspects of supramolecular chirality control as exemplified by self-assembled monolayer networks (SAMNs) formed by a class of chiral building blocks consisting of a triangular conjugated core and alkoxy chains on the periphery. It highlights 2D chirality induction phenomena through a classic "sergeants-and-soldiers" mechanism, in which the inducer is incorporated into a network component, as well as through a "supramolecular host-guest" mechanism, in which the inducer is entrapped in the porous space, leading to counterintuitive chirality reversal. Stereochemical control can be extended to three dimensions too, based on interlayer hydrogen bonding of the same class of building blocks bearing hydroxy groups, exhibiting diastereospecific bilayer formation at both single molecule level and supramolecular level arising from orientation between the top and bottom layers. Finally, we showcase that homochiral SAMNs can also be used as templates for the grafting of in situ generated aryl radicals, by covalent bond formation to the basal graphitic surface, thereby yielding topologically chiral functionalized graphite, and thus extending the potential of chiral SAMNs.

We herein report a unique example of on-surface adaptive self-assembly. A pentagon-shaped macrocycle, cyclic [5]meta-phenyleneacetylene [5]CMPA, is trapped by the adaptive supramolecular network formed by an isosceles triangular molecule, alkoxy substituted dehydrobenzo[14]annulene [14]ISODBA at the liquid/graphite interface, leading to a highly ordered and large-area bicomponent self-assembled molecular network (SAMN), as revealed by scanning tunneling microscopy (STM).

Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface. Herein we report that a trigonal molecule, dehydrobenzo[12]annulene (DBA) derivative having three tetradecyloxy chains and three hydroxy groups in an alternating manner, forms hierarchical triangular clusters of different sizes ranging from 2.4 to 16.4 nm, consisting of 3 to 78 molecules, respectively, at the liquid/graphite interface. The key is the dynamic combination of three different conformational states, which is solvent and concentration dependent. The present knowledge extends design strategies for production of sophisticated hierarchical SAMNs using a single component at the liquid/solid interface., Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface.

This paper deals with map-construction problems for visual localization. Basically, the map is an aggregation of visual landmarks, and it is desirable that such landmarks exist densely and permanen...

Chiral structures created through the adsorption of molecules onto achiral surfaces play pivotal roles in many fields of science and engineering. Here, we present a systematic study of a novel chiral phenomenon on a surface in terms of organizational chirality, that is, meso-isomerism, through coverage-driven hierarchical polymorphic transitions of supramolecular assemblies of highly symmetric π-conjugated molecules. Four coverage-dependent phases of dehydrobenzo[12]annulene were uniformly fabricated on Ag(111), exhibiting unique chiral characteristics from the single-molecule level to two-dimensional supramolecular assemblies. All coverage-driven phase transitions stem from adsorption-induced pseudo-diastereomerism, and our observation of a lemniscate-type (∞) supramolecular configuration clearly reveals a drastic chiral phase transition from an enantiomeric chiral domain to a meso-isomeric achiral domain. These findings provide new insights into controlling two-dimensional chiral architectures on surfaces.

Scanning tunnelling microscope observations at the 1-phenyloctane/graphite interface reveal how chiral structural information at the molecular level is transferred and expressed structurally at the 2D supramolecular level for a porous system. The chirality of self-assembled molecular networks formed by chiral dehydrobenzo[12]annulene (cDBA) derivatives having three chiral chains and three achiral chains, alternatingly, is compared with those of cDBAs having six chiral chains reported previously. While for all cDBAs homochiral surfaces are formed, their handedness is not simply a reflection of the absolute configuration of the stereogenic centres. Both the number of stereogenic centres as well as the length of the achiral chains determine the supramolecular handedness, providing a deep insight into the supramolecular chirality induction mechanisms at play. Moreover, these cDBAs act to induce chirality in porous networks formed by achiral DBAs. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:58 issue:23 pages:7733-7738 ispartof: location:Germany status: published

Two isomers of 9,10-dihydro- as-indacenodithiophenes (DIDTs) and the corresponding diketones having an as-indacene core were synthesized. Their thermal, photophysical, and electrochemical properties were investigated, revealing that they depend on the direction of the fusion of the thiophene rings. For the DIDTs, the effect of the mode of ring fusion on the physical properties is discussed by comparison with the previously reported derivatives of DIDT isomers with an s-indacene core. The observed difference between the highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels of the DIDT isomers is ascribed to the efficiency of π-conjugation, which depends on α- or β-linkage between the terminal thiophenes with the central benzene ring. In addition, the effect of the peripheral aromatic ring (thiophene or benzene) is elucidated by comparison with indeno[2,1- a]fluorene (DIF) bearing an as-indacene core. The HOMO levels of DIDTs are significantly raised compared to that of structurally related DIF because of electron-donating character of the thiophene rings. For the DIDT diketones, structural effect due to the proximate carbonyl groups is discussed by comparison with the isomers with remote carbonyl groups. In diketones bearing proximate carbonyl groups, the LUMO levels are destabilized owing to antibonding interaction between the carbonyl oxygen atoms, resulting in approach of the LUMO and LUMO+1 energy levels.

By using a novel protocol to spatially confine molecules in well-defined small 2D areas, the so-called nanocorrals, we show using scanning tunneling microscopy (STM) how this kind of confinement affects self-assembled molecular network (SAMN) formation at a liquid-solid interface. The 2D lateral confinement, imposed by the size of the nanocorrals, has a clear impact on the phase selectivity of a molecule that can form both low-density and high-density SAMNs, the high-density phase being promoted by the confinement. ispartof: CHEMICAL COMMUNICATIONS vol:55 issue:15 pages:2226-2229 ispartof: location:England status: published

Stereocontrolled multilayer growth of supramolecular porous networks at the interface between graphite and a solution was investigated. For this study, we designed a chiral dehydrobenzo[12]annulene (DBA) building block bearing alkoxy chains substituted at the 2 position with hydroxy groups, which enable van der Waals stabilization in a layer and potential hydrogen-bonding interactions between the layers. Bias voltage-dependent scanning tunneling microscopy (STM) experiments revealed the diastereospecificity of the bilayer with respect to both the intrinsic chirality of the building blocks and the supramolecular chirality of the self-assembled networks. Top and bottom layers within the same crystalline domain were composed of the same enantiomers but displayed opposite supramolecular chiralities.

Controlled covalent functionalization of graphitic surfaces with molecular scale precision is crucial for tailored modulation of the chemical and physical properties of carbon materials. We herein present that porous self-assembled molecular networks (SAMNs) act as nanometer scale template for the covalent electrochemical functionalization of graphite using an aryldiazonium salt. Hexagonally aligned achiral grafted species with lateral periodicity of 2.3, 2.7, and 3.0 nm were achieved utilizing SAMNs having different pore-to-pore distances. The unit cell vectors of the grafted pattern match those of the SAMN. After the covalent grafting, the template SAMNs can be removed by simple washing with a common organic solvent. We briefly discuss the mechanism of the observed pattern transfer. The unit cell vectors of the grafted pattern align along nonsymmetry axes of graphite, leading to mirror image grafted domains, in accordance with the domain-specific chirality of the template. In the case in which a homochiral building block is used for SAMN formation, one of the 2D mirror image grafted patterns is canceled. This is the first example of a nearly crystalline one-sided or supratopic covalent chemical functionalization. In addition, the positional control imposed by the SAMN renders the functionalized surface (homo)chiral reaching a novel level of control for the functionalization of carbon surfaces, including surface-supported graphene. ispartof: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol:142 issue:16 pages:7699-7708 ispartof: location:United States status: published

ispartof: CHEMNANOMAT vol:6 issue:4 pages:550-559 status: published

The covalent functionalization of carbon-based materials through aryldiazonium chemistry has emerged as a powerful tool for physicochemical property modification. However, the characterization tech...

Amazing aromaticity: ChemPlusChem is pleased to present its special issue on novel aromatic compounds, guest-edited by Nazario Martin and Yoshito Tobe. This project was initiated following the 2015 ISNA-16 meeting held in Madrid and the issue features top-quality contributions covering synthesis, properties and applications of acenes, annulenes, azulenes, fullerenes, oligo(thiophene)s, and porphyrin/phthalocyanines.

Thermal comfort is a personal assessment of one's satisfaction with the surroundings. Yet, most thermal comfort delivery mechanisms preclude physiological and psychological precursors to thermal comfort. Accordingly, many people feel either cold or hot in an environment that is supposedly thermally comfortable to most people. To address this issue, this paper proposes to use people's heart rate variability (HRV) as an alternative indicator of thermal comfort. Since HRV is linked to homeostasis, we hypothesize that it could be used to predict people's thermal comfort status. To test our hypothesis, we analyzed statistical, spectral, and nonlinear HRV indices of 17 human subjects doing light office work in a cold, a neutral, and a hot environment. The resulting HRV indices were used as inputs to machine learning classification algorithms. We observed that HRV is distinctively altered depending on the thermal environment and that it is possible to steadfastly predict each subject's thermal environment (cold, neutral, and hot) with up to a 93.7% prediction accuracy. The result of this study implies that it could be possible to design automatic real-time thermal comfort controllers based on people's HRV.

© 2018 American Chemical Society. Chemical and structural defects in otherwise pristine materials can result in either an improved or degraded material performance. Unfortunately, little is known about the role of these defects in complex hierarchical processes, such as self-assembly. Here, the influence of defective surfaces on physisorbed self-assembly occurring at liquid/solid interfaces is investigated. Covalently bound defects on graphite surfaces are generated by electrochemically activating diazonium cations. After creating the defective substrates, a solution containing self-assembling molecules was deposited on the surface. Subsequent scanning probe investigations expose how the chemisorbed molecular units can either be incorporated within a porous hexagonal network, or generate local perturbations in the form of partial or full desorption of the physisorbed molecules. Overall, the chemisorbed molecules alter the local energy landscape for self-assembly to isolate new molecular packing arrangements. With a single-molecule perspective, this work outlines how chemical defects contribute to the formation of metastable assemblies and their evolutionary pathways toward higher-symmetry networks. ispartof: JOURNAL OF PHYSICAL CHEMISTRY C vol:122 issue:42 pages:24046-24054 status: published

The development of smartphones and other portable devices has expanded new ways of communication and collaboration both in private and business settings where there are used e.g. for sharing files and other information. However, this communication is not always secure and can be intercepted by a third party in the vicinity. This paper proposes an intelligent communication control mechanism where the shared information is accessible only within a physically limited space. Normally, existing communication methods based on radio waves (Wi-Fi or Bluetooth) are accessible to anyone within a specific range; thus, they are susceptible to breach and communication eavesdrop beyond walls. Our proposed method is based on an association scheme whereby the sending smartphone can restrict the communication range by controlling an acoustic wave’s magnitude and frequency. Thus, unlike radio waves, it is possible to send the signal to devices located in a specific range, where the client devices exist, after recognizing the distance and angle between devices. Our experiments by sharing signals among smartphones indicate that it is possible to unidirectionally control the sharing range while sharply reducing any possibility to eavesdrop on the communication.

A dehydrobenzo[12]annulene attached by three platinum catecholate units is oxidized chemically or electrochemically to generate mono-, di-, and trications. Similarly, a platinum catecholate complex with a dibenzo[8]annulene framework also generates mono- and dications upon oxidation. On the basis of theoretical and spectroscopic studies with respect to energetic, structural, and magnetic criteria, these dications are deduced to be aromatic, thus demonstrating a new method for stabilizing aromatic dications.

Reductive coupling of 2,7-bis(bromomethyl)naphthalene using phenyllithium gave anti-[22](2,7)naphthalenophane, [23](2,7)naphthalenophane, and [24](2,7)naphthalenophane, the distribution of which was dependent on the reaction conditions. The structure of the first compound was established by X-ray crystallographic analysis. On the basis of the similarity between the NMR and UV spectra of [23](2,7)naphthalenophane with those reported for syn-[22](2,7)naphthalenophane, we conclude that the compound originally assigned to be syn-4 was in fact 6.

Chiral induction in self-assembled monolayers has garnered considerable attention in the recent past, not only due to its importance in chiral resolution and enantioselective heterogeneous catalysis but also because of its relevance to the origin of homochirality in life. Here, we demonstrate the emergence of homochirality in a supramolecular low-density network formed by achiral molecules at the interface of a chiral solvent and an atomically-flat achiral substrate. We focus on the impact of structure and functionality of the adsorbate and the chiral solvent on the chiral induction efficiency in self-assembled physisorbed monolayers, as revealed by scanning tunneling microscopy. Different induction mechanisms are proposed and evaluated, with the assistance of advanced molecular modeling simulations. ispartof: Faraday Discussions vol:204 pages:215-231 ispartof: location:England status: published

A rotaxane composed of a ring molecule having a metaphenylene unit, which swings as a pendulum, and a dianthrylethane unit, which undergoes isomerization in response to external stimuli, and an axle molecule with two different stopper units was synthesized. The rates of the rocking motion, which were switched reversibly, changed substantially by changing the size of the ring component in response to photo- and thermal-stimuli.

The synthesis of a new triaminoguanidinium‐based ligand with three tris‐chelating [NNO]‐binding pockets and C 3 symmetry is described. The reaction of tris‐(2‐pyridinylene‐N‐oxide)triaminoguanidinium salts with zinc(II) formate leads to the formation of cyclic supramolecular coordination compounds which in solution bind fullerenes in their spherical cavities. The rapid encapsulation of C60 can be observed by NMR spectroscopy and single‐crystal X‐ray diffraction and is verified using computation., Cage bound: Synthesis of a new triaminoguanidinium‐based ligand with three tris‐chelating [NNO] binding pockets and C 3‐symmetry is described. Reaction with zinc(II) formate leads to the formation of cyclic supramolecular coordination compounds that in solution are able to bind fullerenes in their spherical cavities. The rapid encapsulation of C60 is observed by NMR spectroscopy and X‐ray diffraction and is validated by DFT.

We herein investigated the effect of the number of alkoxy chains on the two-dimensional self-assembly of a trigonal molecular building block. To this end, a dehydrobenzo[12]annulene (DBA) derivativ...

We present here the construction of a self-assembled two-dimensional network at the liquid/solid interface using a hexagonal pyridine macrocycle which binds an organic cation in its intrinsic porous space by electrostatic interactions. For this purpose, a hexagonal pyridinylene-butadiynylene macrocycle (PyBM) having six octyloxymethyl groups, PyBM-C8, was synthesized. As guests, tropylium (Tr) tetrafluoroborate and trioxatriangulenium (TOTA) hexafluorophosphate were used. In this study, we focused on (i) the network patterns of PyBM-C8 which change in response to its concentration and (ii) the position of the guest immobilized in the porous space of the macrocycle. Scanning tunneling microscopy (STM) observations at the interface of 1,2,4-trichlorobenzene (TCB) and highly oriented pyrolytic graphite (HOPG) revealed that PyBM-C8 formed four different polymorphs, oblique, loose hexagonal, linear, and rectangular, depending on the solute concentration and annealing treatment. Solvent TCB molecules are likely coadsorbed to not only the intrinsically porous space of PyBM-C8 (internal TCB) but also the space outside of the macrocycle between its alkyl chains (external TCB) in most of the cases. Upon adding the guest cation, whereas small Tr was not visualized in the pore due to size mismatching, larger TOTA was clearly observed in each pore. In addition, based on high-resolution STM images of the rhombus packing pattern of PyBM-C8, we revealed experimentally that TOTA was placed at an off-center position of the deformed hexagonal macrocyclic core in the rhombus pattern. On the basis of the molecular mechanics calculations, we hypothesize that the off-center location of TOTA is due to deformation of the hexagonal macrocycle through interaction with two external TCB molecules located at opposite edges of the macrocyclic core. Symmetry breaking of the macrocyclic host framework induced by coadsorbed surrounding solvent molecules thus plays a significant role in host-guest complexation at the liquid/solid interface. ispartof: LANGMUIR vol:35 issue:47 pages:15051-15062 ispartof: location:United States status: published

Grafting of aryl radicals generated by electrochemical reduction of aryldiazonium salts has been extensively studied on various surfaces. However, there exists two unclear aspects; the first one is the generality of the blocking ability of simple functional groups toward multilayer growth, and the second one is the electronic impact of substituent groups of aryl radicals on grafting efficiency. To address these aspects, we have studied the electrochemical functionalization of graphite using aryldiazonium salts having electron-donating or electron-withdrawing groups at the 3,4,5-positions. Atomic force microscopy investigation of the functionalized surfaces revealed the formation of monolayers for all aryldiazonium salts, and thus, nitro, carboxy, ester, methyl, and methoxy groups at the 3,4,5-positions of the benzene ring suppress polyaryl growth. The degree of grafting estimated by scanning tunneling microscopy imaging and Raman spectroscopy of the functionalized surfaces depends on the electronic state of the aryl radicals, in which the radicals with electron-donating groups show a high degree of functionalization, whereas those with electron-withdrawing groups exhibit a low degree of functionalization. We discuss several possibilities that affect grafting density. Though there are several factors, we hypothesize that one factor to explain the observed reactivity trend is the electronic property of the aryl radicals, namely, the relative position of the singly occupied molecular orbital energy levels of the aryl radicals with respect to the graphite Fermi energy level. ispartof: LANGMUIR vol:35 issue:6 pages:2089-2098 ispartof: location:United States status: published

An approach for nanoscale covalent functionalization of graphite surfaces employing self-assembled molecular monolayers of n-alkanes as templating masks is presented. Linearly aligned aryl groups with a lateral periodicity of 5 or 7 nm are demonstrated utilizing molecular templates of different lengths. The key feature of this approach is the use of a phase separated solution double layer consisting of a thin organic layer containing template molecules topped by an aqueous layer containing aryldiazonium molecules capable of electrochemical reduction to generate aryl radicals which bring about surface grafting. Upon sweeping of the potential, lateral displacement dynamics at the n-alkane terminal edges acts in conjunction with electrochemical diffusion to result in templated covalent bond formation in a linear fashion. This protocol was demonstrated to be applicable to linear grafting of graphene. The present processing described herein is useful for the realization of rationally designed nanoscale materials. ispartof: ACS NANO vol:12 issue:11 pages:11520-11528 ispartof: location:United States status: published

© 2018 American Chemical Society. Understanding structure-efficiency relationships in chiral recognition and chirality transfer constitutes an important step toward the rational design of improved chiral probes and chirality auxiliaries or inducers. Recently discovered enantioselective host-guest adsorption opened a new pathway toward the enantioselective reconstruction of on-surface monolayers. In this study, we explored the importance of size matching between host cavity and chiral guest for the efficiency of chiral recognition and subsequent chirality induction in the initially racemic host. ispartof: JOURNAL OF PHYSICAL CHEMISTRY C vol:122 issue:15 pages:8228-8235 status: published

Rotaxanes consisting of achiral axle and achiral ring components can possess supramolecular chirality due to their unique geometrical architectures. To synthesize such chiral rotaxanes, we adapted a prerotaxane method based on aminolysis of a metacyclophane type prerotaxane that had planar chirality, which is composed of an achiral stopper unit and a crown ether type ring component. The prerotaxanes were well resolved using chiral HPLC into a pair of enantiomerically pure prerotaxanes, which were transferred into corresponding chiral rotaxanes, respectively. Obtained chiral rotaxanes were revealed to have considerable enantioselectivity.

To demonstrate key roles of multiple interactions between multiple components and multiple phases in the formation of an uncommon self-assembling pattern, we present here the construction of a porous hexagonal star (h-star) structure using a trigonal molecular building block at the liquid/ solid interface. For this purpose, self-assembly of hexaalkoxysubstituted dehydrobenzo[12]annulene derivatives DBA-OCns was investigated at the tetradecane/graphite interface by means of scanning tunneling microscopy (STM). Monolayer structures were significantly influenced by coadsorbed tetradecane molecules depending on the alkyl chains length (C13−C16) of DBA-OCn. However, none of DBA-OCn molecules formed the expected trigonal complexes, indicating that an additional driving force is necessary for the formation of the trigonal complex and its assembly into the h-star structure. As a first approach, we employed the “guest induced structural change” for the formation of the h-star structure. In the presence of two guest molecules, nonsubstituted DBA and hexakis(phenylethynyl)benzene which fit the respective pores, an h-star structure was formed by DBAOC15 at the tetradecane/graphite interface. Moreover, a tetradecane molecule was coadsorbed between a pair of alkyl chains of DBA-OC15, thereby blocking the interdigitation of the alkyl chain pairs. Therefore, the h-star structure results from the selfassembly of the four molecular components including the solvent molecule. The second approach is based on aggregation of perfluoroalkyl chains via fluorophilicity of DBA-F, in which the perfluoroalkyl groups are substituted at the end of three alkyl chains of DBA-OCn via p-phenylene linkers. A trigonal complex consisting of DBA-F and three tetradecane molecules formed an h-star structure, in which the perfluoroalkyl groups that orient into the alkane solution phase aggregated at the hexagonal pore via fluorophilicity. The present result provides useful insight into the design and control of complex molecular self-assembly at the liquid/solid interface. ispartof: Langmuir vol:31 issue:25 pages:7032-7040 ispartof: location:United States status: published

A tetramesityl derivative of hitherto unknown tetracyclopenta[def,jkl,pqr,vwx]tetraphenylene (TCPTP), which is a potential tetraradicaloid hydrocarbon, was synthesized. Theoretical calculations based on spin-flip time-dependent density functional theory predict that the closed-shell D2h form of TCPTP is more stable than the open-shell D4h form with its slightly tetraradical character. The tetramesityl derivative (Mes)4 -TCPTP exhibits remarkable antiaromaticity as a result of the peripheral 20-π-electron circuit, which causes an absorption maximum at a long wavelength and a small HOMO-LUMO gap. In solution, (Mes)4 -TCPTP most likely adopts rapidly equilibrating D2h structures that interconvert via the D4h transition state. X-ray crystallographic analysis showed (Mes)4 -TCPTP as an approximate D2h structure.

The dimesityl derivative of fluoreno[2,3-b]fluorene (6b) was synthesized and its structure and physical properties were investigated to elucidate the effects of its enhanced open-shell character, which was predicted theoretically in comparison with the smaller congener indeno[2,1-b]fluorene (5b). All structural and physical properties are in accordance with the theoretical predictions and can be interpreted in terms of the resonance contributors. The most remarkable spectroscopic property is the larger excitation energy of 24π-electron hydrocarbon 6b than that of 20π-electron system 5b in their lowest energy absorption bands of electronic spectra, a trend that is contrary to the well-known feature for common, alternant aromatic hydrocarbons. The theoretical basis of this unusual behavior was elucidated on the basis of the balance between the diradical character, exchange integral, and HOMO-LUMO gap and was confirmed by a complete-active-space configuration-interaction method with two electrons in two orbitals for the corresponding parent hydrocarbons 5a and 6a.

We report on the design and fabrication of a four-component supramolecular network using the ‘core–shell’ approach. Each ‘core’ component templates the formation of an outer ‘shell’ leading to formation of three concentric ‘shells’ around the central guest. The ‘shells’ are formed only in presence of guests thus demonstrating remarkable selectivity in molecular recognition. crosscheck: This document is CrossCheck deposited related_data: Supplementary Information identifier: Kunal S. Mali (ORCID) identifier: Yoshito Tobe (ORCID) identifier: Steven De Feyter (ORCID) copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) history: Received 17 November 2016; Accepted 20 December 2016; Advance Article published 5 January 2017; Version of Record published 17 January 2017 ispartof: Chemical Communications vol:53 issue:6 pages:1108-1111 ispartof: location:England status: published