Controlled Electrodissolution of Polyelectrolyte Multilayers: A Platform Technology Towards the Surface‐Initiated Delivery of Drugs

A novel method for the electrochemical dissolution of polyelectrolyte multilayers from the surface of an electrode for applications in controlled drug delivery is reported. Biodegradable and biocompatible multilayer films based on poly(L ‐lysine) and heparin have been selected as a model system, and have been built on an indium tin oxide semiconductor substrate. The build‐up and dissolution processes of the multilayers is followed by electrochemical optical waveguide light mode spectroscopy. The formation and stability of the polyelectrolyte multilayers have been found to depend on the applied potential and the ionic strength of the buffer. The application of potentials above a threshold of 1.8 V induces dissolution, which follows single‐exponential kinetics, of the polyelectrolyte multilayer film. The rate of this process can be varied by an on–off profile of the potential, leading to the controlled release of heparin into the bulk. Atomic force microscopy investigations show that the electrodissolution of the polyelectrolyte multilayers is a local phenomenon that leads to the formation of nanoporous films.     

A Novel Polymeric Ionomer as a Potential Biomaterial: Crystallization Behavior,Degradation, and In‐Vitro Cellular Interactions

To evaluate the potential of polyester‐based ionomers as biomaterials, we have characterized them in terms of crystallization behavior, degradation, and in‐vitro cellular interactions. The polymers used are poly(butylene succinate)‐based ionomers (PBSis) with 1 to 5 mol‐% dimethyl 5‐sodium sulfoisophthalate. Even a few incorporated ionic groups significantly decreases the folding surface energy, indicating that folding into crystalline lamellae is more difficult for chains restricted by ionic aggregates. Transmission electron microscopy (TEM) does not reveal any distinct aggregation of ionic clusters following hydrolytic degradation, which suggests that the physical crosslinkage due to ionic interactions is vulnerable to hydrolysis. The in‐vitro cellular interactions of polyester‐based ionomers is assessed by the culture of human dermal fibroblasts with PBSi extracts or in direct contact with the PBSi films. Cells on PBSi films and in their extracts exhibit appropriate specific growth rates and normal metabolic function regardless of the incorporated ionic content compared with poly[(D ,L ‐lactic acid)‐co‐(glycolic acid)] (75:25, PLGA), which is well known to be biocompatible. The cells growing on PBSi films spread to a sufficient extent, displaying relatively active filopodial growth, as compared to that of parent PBS. These results suggest that the conspicuous topology and hydrophilic nature of the ionomer surface affect cellular interactions, and that this ionomer therefore has potential applications as a biomaterial.     

Primary Neuron/Astrocyte Co‐Culture on Polyelectrolyte Multilayer Films: A Template for Studying Astrocyte‐Mediated Oxidative Stress in Neurons

We engineered patterned co‐cultures of primary neurons and astrocytes on polyelectrolyte multilayer (PEM) films without the aid of adhesive proteins/ligands to study the oxidative stress mediated by astrocytes on neuronal cells. A number of studies have explored engineering co‐culture of neurons and astrocytes predominantly using cell lines rather than primary cells owing to the difficulties involved in attaching primary cells onto synthetic surfaces. To our knowledge this is the first demonstration of patterned co‐culture of primary neurons and astrocytes for studying neuronal metabolism. In our study, we used synthetic polymers, namely poly(diallyldimethylammoniumchloride) (PDAC) and sulfonated poly(styrene) (SPS) as the polycation and polyanion, respectively, to build the multilayers. Primary neurons attached and spread preferentially on SPS surfaces, while primary astrocytes attached to both SPS and PDAC surfaces. SPS patterns were formed on PEM surfaces, either by microcontact printing SPS onto PDAC surfaces or vice‐versa, to obtain patterns of primary neurons and patterned co‐cultures of primary neurons and astrocytes. We further used the patterned co‐culture system to study the neuronal response to elevated levels of free fatty acids as compared to the response in separated monoculture by measuring the level of reactive oxygen species (ROS; a widely accepted marker of oxidative stress). The elevation in the ROS levels was observed to occur earlier in the patterned co‐culture system than in the separated monoculture system. The results suggest that this technique may provide a useful tool for engineering neuronal co‐culture systems, that may more accurately capture neuronal function and metabolism, and thus could be used to obtain valuable insights into neuronal cell function and perhaps even the pathogenesis of neurodegenerative diseases.     

Biofunctional Polyelectrolyte Multilayers and Microcapsules: Control of Non‐Specific and Bio‐Specific Protein Adsorption

Layers of the polyelectrolytes poly(allylamine hydrochloride) (PAH, polycationic) and poly(styrene sulfonate) (PSS, polyanionic) are consecutively adsorbed on flat silicon oxide surfaces, forming stable, ultrathin multilayer films. Subsequently, a final monolayer of the polycationic copolymer poly(L ‐lysine)‐graft‐poly(ethylene glycol) (PLL‐g‐PEG) is adsorbed onto the PSS‐terminated multilayer in order to impart protein resistance to the surface. The growth of each of the polyelectrolyte layers and the protein resistance of the resulting [PAH/PPS]_n(PLL‐g‐PEG) multilayer (n = 1–4) are followed quantitatively ex situ using X‐ray photoelectron spectroscopy and in situ using real‐time optical‐waveguide lightmode spectroscopy. In a second approach, the same type of [PAH/PSS]_n(PLL‐g‐PEG) multilayer coatings are successfully formed on the surface of colloidal particles in order to produce surface‐functionalized, hollow microcapsules after dissolution of the core materials (melamine formaldehyde (MF) and poly(lactic acid) (PLA; colloid diameters: 1.2–20 μm). Microelectrophoresis and confocal laser scanning microscopy are used to study multilayer formation on the colloids and protein resistance of the final capsule. The quality of the PLL‐g‐PEG layer on the microcapsules depends on both the type of core material and the dissolution protocols used. The greatest protein resistance is achieved using PLA cores and coating the polyelectrolyte microcapsules with PLL‐g‐PEG after dissolution of the cores. Protein adsorption from full serum on [PAH/PPS]_n(PLL‐g‐PEG) multilayers (on both flat substrates and microcapsules) decreases by three orders of magnitude in comparison to the standard [PAH/PPS]_n layer. Finally, biofunctional capsules of the type [PAH/PPS]_n(PLL‐g‐PEG/PEG‐biotin) (top copolymer layer with a fraction of the PEG chains end‐functionalized with biotin) are produced which allow for specific recognition and immobilization of controlled amounts of streptavidin at the surface of the capsules. Biofunctional multilayer films and capsules are believed to have a potential for future applications as novel platforms for biotechnological applications such as biosensors and carriers for targeted drug delivery.     

Structural Transformations during Formation of Quasi‐Amorphous BaTiO3

A model of structural transformations of amorphous into quasi‐amorphous BaTiO₃ is suggested. The model is based on previously published data and on X‐ray photoelectron spectroscopy data presented in the current report. Both amorphous and quasi‐amorphous phases of BaTiO₃ are made up of a network of slightly distorted TiO₆ octahedra connected in three different ways: by apices (akin to perovskite), edges, and faces. Ba ions in these phases are located in the voids between the octahedra, which is a nonperovskite environment. These data also suggest that Ba ions compensate electrical‐charge imbalance incurred by randomly connected octahedra and, thereby, stabilize the TiO₆ network. Upon heating, the edge‐to‐edge and face‐to‐face connections between TiO₆ octahedra are severed and then reconnected via apices. Severing the connections between TiO₆ octahedra requires a volume increase, suppression of which keeps some of the edge‐to‐edge and face‐to‐face connections intact. Transformation of the amorphous thin films into the quasi‐amorphous phase occurs during pulling through a steep temperature gradient. During this process, the volume increase is inhomogeneous and causes both highly anisotropic strain and a strain gradient. The strain gradient favors breaking those connections, which aligns the distorted TiO₆ octahedra along the direction of the gradient. As a result, the structure becomes not only anisotropic and non‐centrosymmetric, but also acquires macroscopic polarization. Other compounds may also form a quasi‐amorphous phase, providing that they satisfy the set of conditions derived from the suggested model.     

Thermo‐Mechanical Responses of Liquid‐Crystal Networks with a Splayed Molecular Organization

Films of liquid‐crystal networks with a splayed molecular alignment over their cross‐section display a well‐controlled deformation as a function of temperature. The deformation can be explained in terms of differences in thermal expansion depending on the average molecular orientation of the mesogenic centers of the monomeric units. The thermal expansion of the anisotropic polymers has been characterized as a function of their molecular structure and the polymerization conditions. As a reference, films with an in‐plane 90° twist have also been studied and compared with the splayed, out‐of‐plane molecular rotation. The twisted films show a complex macroscopic deformation owing to the formation of saddle‐like geometries, whereas the deformation of the splayed structured is smooth and well controlled. The deformation behavior is anticipated to be of relevance for polymer‐based microelectromechanical system (MEMS) technology.     

Structural Modifications to Polystyrene via Self‐Assembling Molecules

We have previously reported that small quantities of self‐assembling molecules known as dendron rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS). These molecules spontaneously assemble into supramolecular nanoribbons that can be incorporated into bulk PS in such a way that the orientation of the polymer is significantly enhanced when mechanically drawn above the glass‐transition temperature. In the current study, we more closely evaluate the structural role of the DRC nanoribbons in PS by investigating the mechanical properties and deformation microstructures of polymers modified by self‐assembly. In comparision to PS homopolymer, PS containing small amounts (≤ 1.0 wt.‐%) of self‐assembling DRC molecules exhibit greater Charpy impact strengths in double‐notch four‐point bending and significantly greater elongations to failure in uniaxial tension at 250 % prestrain. Although the DRC‐modified polymer shows significantly smaller elongations to failure at 1000 % prestrain, both low‐ and high‐prestrain specimens maintain tensile strengths that are comparable to those of the homopolymer. The improved toughness and ductility of DRC‐modified PS appears to be related to the increased stress whitening and craze density that was observed near fracture surfaces. However, the mechanism by which the self‐assembling DRC molecules toughen PS is different from that of conventional additives. These molecules assemble into supramolecular nanoribbons that enhance polymer orientation, which in turn modifies crazing patterns and improves impact strength and ductility.     

A Smart Supramolecular Hydrogel Exhibiting pH‐Modulated Viscoelastic Properties

The macroscopic viscoelastic properties of a physical hydrogel are reversibly modulated by tuning the microscopic hydrogen‐bonding interactions with pH. The hydrogel forms at a rather low concentration of the multi‐pyridyl‐based gelator, N, N′, N″‐tris(3‐pyridyl)trimesic amide. The yield stress of the hydrogel is greatly enhanced from 10 to 769 Pa by changing the pH from 7.0 to 5.0. At pH 7.0, the amide molecules are assembled into an ordered structure as a result of the hydrogen bonds between the amide N–H bond and the nitrogen on the pyridyl group (N–H…Py). Fourier transform (FT) IR spectroscopy indicates that hydrogen bonds of N–H…Py are partially broken because the pyridyl groups are partly protonated at pH 5.0. This condition leads to a highly branched and homogeneous fibrillar network, which is confirmed by X‐ray diffraction (XRD) measurements and field‐emission scanning electron microscopy (FESEM) images. Highly branched fibrillar networks create more compartments and greatly increase the interfacial tension that is required to hold the solvent in the gel, thereby increasing the yield stress to 769 Pa. By further increasing the acidity of the hydrogel to pH < 3.0, the gel becomes a sol. Both the change in the viscoelastic properties and the sol–gel transition are reversible and controllable in the material.     

Cover Picture: Structural Modifications to Polystyrene via Self‐Assembling Molecules (Adv. Funct. Mater. 3/2005)

The cover shows tensile failure of a sample of pure polystyrene (left), and a polystyrene sample with greater impact strength containing 1% by weight of dispersed nanoribbons (right), as reported in work by Stupp and co‐workers on p. 487. The nanoribbons are formed by self‐assembly of molecules known as dendron rodcoils (DRCs) in styrene monomer, resulting in the formation of a gel. This gel can then be polymerized thermally. We have previously reported that small quantities of self‐assembling molecules known as dendron rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS). These molecules spontaneously assemble into supramolecular nanoribbons that can be incorporated into bulk PS in such a way that the orientation of the polymer is significantly enhanced when mechanically drawn above the glass‐transition temperature. In the current study, we more closely evaluate the structural role of the DRC nanoribbons in PS by investigating the mechanical properties and deformation microstructures of polymers modified by self‐assembly. In comparision to PS homopolymer, PS containing small amounts (≤ 1.0 wt.‐%) of self‐assembling DRC molecules exhibit greater Charpy impact strengths in double‐notch four‐point bending and significantly greater elongations to failure in uniaxial tension at 250 % prestrain. Although the DRC‐modified polymer shows significantly smaller elongations to failure at 1000 % prestrain, both low‐ and high‐prestrain specimens maintain tensile strengths that are comparable to those of the homopolymer. The improved toughness and ductility of DRC‐modified PS appears to be related to the increased stress whitening and craze density that was observed near fracture surfaces. However, the mechanism by which the self‐assembling DRC molecules toughen PS is different from that of conventional additives. These molecules assemble into supramolecular nanoribbons that enhance polymer orientation, which in turn modifies crazing patterns and improves impact strength and ductility.     

Fabrication of Metal Oxides Occluded in Ordered Mesoporous Hosts via a Solid‐State Grinding Route: The Influence of Host–Guest Interactions

Solid‐state grinding is a simple and effective method to include guest species into the channels of ordered mesoporous materials with a different degree of filling. After calcination, a monolayer or several monolayers of guest species can not only form highly dispersed oxide species and other surface species on the hosts whether the template is occluded in the channels or not, but the guest species can also fill the mesoporous channels in the host and thus lead to nanowires or nanoarrays. Solid‐state salt inclusion is faster and more convenient than other inclusion routes. The absence of a solvent not only saves the time otherwise needed for evaporation but also leads to a higher degree of filling through a simple inclusion step as the void space in the pores is not occupied by the solvent. Also, the lack of competitive adsorption of solvent molecules enhances the interaction between the guest species included and the silica wall, which facilitates the high dispersion of oxide species. However, host–guest interactions that are too strong may disturb the self‐crystallization of guest species in the mesopores leading to imperfect nanocasting of the mesostructure.     

Deformation of Top‐Down and Bottom‐Up Silver Nanowires

Atomistic simulations are employed to probe the deformation behavior of experimentally observed top‐down and bottom‐up face‐centered cubic silver nanowires. Stable, <110> oriented nanowires with a rhombic and truncated‐rhombic cross section are considered, representative of top‐down geometries, as well as the multiply twinned pentagonal nanowire that is commonly fabricated in a bottom‐up approach. The tensile deformation of a stable, experimentally observed structure is simulated to failure for each nanowire structure. A detailed, mechanistic explanation of the initial defect nucleation is provided for each nanowire. The three geometries are shown to exhibit different levels of strength and to deform by a range of mechanisms depending on the nanowire structure. In particular, the deformation behavior of top‐down and bottom‐up nanowires is shown to be fundamentally different. The yield strength of nanowires ranging from 1 to 25 nm in diameter is provided and reveals that in addition to cross‐sectional diameter, the strength of the nanowires is strongly tied to the structure. This study demonstrates that nanowire structure and size may be tailored for specific mechanical requirements in nanometer‐scale devices.     

Highly Efficient Orange and Green Solid‐State Light‐Emitting Electrochemical Cells Based on Cationic IrIII Complexes with Enhanced Steric Hindrance

Highly efficient orange and green emission from single‐layered solid‐state light‐emitting electrochemical cells based on cationic transition‐metal complexes [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ (where ppy is 2‐phenylpyridine, dFppy is 2‐(2,4‐difluorophenyl)pyridine, and sb is 4,5‐diaza‐9,9′‐spirobifluorene) is reported. Photoluminescence measurements show highly retained quantum yields for [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂ sb]PF₆ in neat films (compared with quantum yields of these complexes dispersed in m‐bis(N‐carbazolyl)benzene films). The spiroconfigured sb ligands effectively enhance the steric hindrance of the complexes and reduce the self‐quenching effect. The devices that use single‐layered neat films of [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ achieve high peak external quantum efficiencies and power efficiencies of 7.1 % and 22.6 lm W^–1) at 2.5 V, and 7.1 % and 26.2 lm W^–1 at 2.8 V, respectively. These efficiencies are among the highest reported for solid‐state light‐emitting electrochemical cells, and indicate that cationic transition‐metal complexes containing ligands with good steric hindrance are excellent candidates for highly efficient solid‐state electrochemical cells.     

Oligothiophene‐Functionalized Truxene: Star‐Shaped Compounds for Organic Field‐Effect Transistors

Organic field‐effect transistors (OFETs) based on oligothiophene‐functionalized truxene derivatives have been fabricated for use as novel star‐shaped organic semiconductors in solution‐processible organic electronics. The electronic and optical properties of compounds 1 – 3 , with increasing numbers of thiophene rings at each of the three branches, have been investigated using scanning electron microscopy (SEM), X‐ray diffraction measurements, and ultraviolet–visible (UV‐vis) and photoluminescence spectroscopies. The results show that with a stepwise increase of the thiophene rings at every branch, a transition from a polycrystalline to an amorphous state is observed. The characteristics of compounds 1 , 2 , and 3 used for OFETs exhibit a significant difference. The mobility depends greatly on the morphology in the solid state, and decreases in going from 1 to 3 . Mobilities up to 1.03 × 10^–3 cm² V^–1 s^–1 and an on/off ratio of about 10³ for compound 1 have been achieved; these are the highest values for star‐shaped organic semiconductors used for OFETs so far. All the results demonstrate that the truxene core of the oligothiophene‐functionalized truxene derivatives not only extends the π‐delocalized system, but also leads to high mobilities for the compounds.     

Thermal and Structural Characterizations of Individual Single‐, Double‐, and Multi‐Walled Carbon Nanotubes

Thermal conductance measurements of individual single‐ (S), double‐ (D), and multi‐ (M) walled (W) carbon nanotubes (CNTs) grown using thermal chemical vapor deposition between two suspended microthermometers are reported. The crystal structure of the measured CNT samples is characterized in detail using transmission electron microscopy (TEM). The thermal conductance, diameter, and chirality are all determined on the same individual SWCNT. The thermal contact resistance per unit length is obtained as 78–585 m K W^?1 for three as‐grown 10–14 nm diameter MWCNTs on rough Pt electrodes, and decreases by more than 2 times after the deposition of amorphous platinum–carbon composites at the contacts. The obtained intrinsic thermal conductivity of approximately 42–48, 178–336, and 269–343 W m^?1 K^?1 at room‐temperature for the three MWCNT samples correlates well with TEM‐observed defects spaced approximately 13, 20, and 29 nm apart, respectively; whereas the effective thermal conductivity is found to be limited by the thermal contact resistance to be about 600 W m^?1 K^?1 at room temperature for the as‐grown DWCNT and SWCNT samples without the contact deposition.     

Origin of the Reduced Fill Factor and Photocurrent in MDMO‐PPV:PCNEPV All‐Polymer Solar Cells

The photogeneration mechanism in blends of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV) and poly[oxa‐1,4‐phenylene‐(1‐cyano‐1,2‐vinylene)‐(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene)‐1,2‐(2‐cyanovinylene)‐1,4‐phenylene] (PCNEPV) is investigated. The photocurrent in the MDMO‐PPV:PCNEPV blends is strongly dependent on the applied voltage as a result of a low dissociation efficiency of the bound electron–hole pairs. The dissociation efficiency is limited by low carrier mobilities, low dielectric constant, and the strong intermixing of the polymers, leading to a low fill factor and a reduced photocurrent at operating conditions. Additionally, electrons trapped in the PCNEPV phase recombine with the mobile holes in the MDMO‐PPV phase at the interface between the two polymers, thereby affecting the open‐circuit voltage and increasing the recombination losses. At an intensity of one sun, Langevin recombination of mobile carriers dominates over trap‐assisted recombination.     

Mechanical Properties of Functionalized Single‐Walled Carbon‐Nanotube/Poly(vinyl alcohol) Nanocomposites

Nanocomposites based on semi‐crystalline poly(vinyl alcohol) (PVA) and well‐dispersed chemically functionalized single‐walled carbon nanotubes are combined through simple mixing. The interaction between the nanotubes and the polymer matrix is studied using optical and thermal methods. Significant enhancement of the mechanical properties is obtained for the functionalized‐nanotube‐based composites. These results imply that promoting nanotube dispersion and strong interfacial bonding through adequate functionalization of nanotubes improves the load transfer from the matrix to the reinforcing phase.     

Composition‐ and Shape‐Controlled Synthesis and Optical Properties of ZnxCd1–xS Alloyed Nanocrystals

Composition‐tunable Zn_xCd_1–xS alloyed nanocrystals have been synthesized by a new approach consisting of thermolyzing a mixture of cadmium ethylxanthate (Cd(exan)₂) and zinc ethylxanthate (Zn(exan)₂) precursors in hot, coordinating solvents at relatively low temperatures (180–210 °C). The composition of the alloyed nanocrystals was accurately adjusted by controlling the molar ratio of Cd(exan)₂ to Zn(exan)₂ in the mixed reactants. The alloyed Zn_xCd_1–xS nanocrystals prepared in HDA/TOP (HDA: hexadecylamine; TOP: trioctylphosphine) solution exhibit composition‐dependent shape and phase structures as well as composition‐dependent optical properties. The shape of the Zn_xCd_1–xS nanocrystals changed from dot to single‐armed rod then to multi‐armed rod with a decrease of Zn content in the ternary nanoparticles. The alloying nature of the Zn_xCd_1–xS nanocrystals was consistently confirmed by the results of high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), and UV‐vis absorption and photoluminescence (PL) spectroscopy. Further, the shape‐controlled synthesis of the ternary alloyed nanocrystals was realized by selecting appropriate solvents. Uniform nanodots in the whole composition range were obtained from TOPO/TOP solution, (TOPO: trioctylphosphine oxide) and uniform nanorods in the whole composition range were prepared from HDA/OA solution (OA: octylamine). The effect of the reaction conditions, such as solvent, reaction temperature, and reaction time, on the PL spectra of the alloyed Zn_xCd_1–xS nanocrystals was also systematically studied, and the reaction conditions were optimized for improving the PL properties of the nanocrystals.     

Vertically Aligned Nanocomposite Thin Films as a Cathode/Electrolyte Interface Layer for Thin‐Film Solid Oxide Fuel Cells

A thin layer of a vertically aligned nanocomposite (VAN) structure is deposited between the electrolyte, Ce_0.9Gd_0.1O_1.95 (CGO), and the thin‐film cathode layer, La_0.5Sr_0.5CoO₃ (LSCO), of a thin‐film solid‐oxide fuel cell (TFSOFC). The self‐assembled VAN nanostructure contains highly ordered alternating vertical columns of CGO and LSCO formed through a one‐step thin‐film deposition process that uses pulsed laser deposition. The VAN structure significantly improves the overall performance of the TFSOFC by increasing the interfacial area between the electrolyte and cathode. Low cathode polarization resistances of 9 × 10^?4 and 2.39 Ω were measured for the cells with the VAN interlayer at 600 and 400 °C, respectively. Furthermore, anode‐supported single cells with LSCO/CGO VAN interlayer demonstrate maximum power densities of 329, 546, 718, and 812 mW cm^?2 at 550, 600, 650, and 700 °C, respectively, with an open‐circuit voltage (OCV) of 1.13 V at 550 °C. The cells with the interlayer triple the overall power output at 650 °C compared to that achieved with the cells without an interlayer. The binary VAN interlayer could also act as a transition layer that improves adhesion and relieves both thermal stress and lattice strain between the cathode and the electrolyte.     

Guest‐Induced Chirality in the Ferrimagnetic Nanoporous Diamond Framework Mn3(HCOO)6

Chiral magnets are obtained by inclusion of chiral guest molecules into the channels of an achiral nanoporous ferrimagnet consisting of the Mn₃(HCOO)₆ ( 1 ) framework. Insertion of the R or the S enantiomer of 2‐chloropropan‐1‐ol (CH₃C*HClCH₂OH) in the chiral pores of the previously emptied framework (space group P2₁/c) results in the two corresponding chiral solids ( 1R and 1S , space group P2₁), while insertion of a racemic mixture of the two enantiomers retains the achirality of the host for the meso solid ( 1RS , space group P2₁/c). The R guest is ordered in the M channels while the S guest is ordered in the P channels. In contrast, the R guests in the P channels and the S guests in the M channels are disordered on two crystallographic orientations. For the racemic mixture of the two enantiomers in 1RS , random disorder of guests in both channels is observed. Thus, the localization of the guest molecule depends on the nature of the surface to recognize the guest of a particular chirality. The guest inclusion compounds are thermally stable. The 1R and 1S compounds are optically active. All the compounds adopt a ferrimagnetic ground state. Compared to the host framework of 1 without guest, the Curie temperature decreases for both 1R and 1S but increases for 1RS . The additional interactions between the framework and the inserted guest alcohols strengthen the lattice via hydrogen bonds and other electrostatic forces, and it might account for the significant lowering of the lattice contribution as well as the magnetic component to the specific heat capacity upon guest loading.