Amperometric Detection of Sub-ppm Formaldehyde Using Single-Walled Carbon Nanotubes and Hydroxylamines: A Referenced Chemiresistive System

We report amperometric detection of formaldehyde (HCHO) using hydroxylamine hydrochloride and single-walled carbon nanotubes (SWCNTs). Hydroxylamine hydrochloride reacts with HCHO to emit HCl vapor, which injects a hole carrier into semiconducting SWCNTs. The increase of conductivity in SWCNTs is easily monitored using an ohmmeter. The debundling of SWCNTs with a metallo-supramolecular polymer (MSP) increased the active surface area in the SWCNTs network, leading to excellent sensitivity to HCHO with a limit of detection (LoD) of 0.016 ppm. The response of sensor is reversible, and the sensor is reusable. The selectivity to HCHO is 10⁵–10⁶ times higher than interferences with other volatiles such as water, methanol, and toluene. Moreover, false-positive responses caused by a significant variation of humidity and/or temperature are successfully discriminated from true-positive responses by using two sensors, one with and the other without hydroxylamine hydrochloride, in a referenced system

Designing Lower Critical Solution Temperature Behavior into a Discotic Small Molecule

Design and analysis of amphiphilic small molecules exhibiting lower critical solution temperature (LCST) behavior is reported. 2,3,6,7,10,11-Hexakis[2-(<i>N</i>,<i>N</i>-dialkylamino)ethoxy] triphenylenes containing hydrophilic groups attached at their discotic core were prepared, and the LCST behavior of their solutions was studied using fluorescence spectrophotometry and ¹H NMR spectroscopy. ¹H NMR spin−lattice relaxation times were used to assess the rotational mobility of molecules below and above the clouding point. The impact on the LCST of supramolecular π−π stacking forces introduced by the triphenylene (TP) core was studied. The operation of the LCST phenomenon was found not to depend significantly on stacking of TP moieties. This process in small molecular species offers several advantages over the polymer-originated phenomenon. For instance, enabling an analogue of the LCST transition in dye molecules might allow the design of novel optical devices by permitting previously unavailable specific aggregated states

NMR Spectroscopic Determination of Enantiomeric Excess Using Small Prochiral Molecules

The use of chiral auxiliaries, which derivatize enantiomers to diastereomers, is an established technique for NMR spectroscopic analysis of chirality and enantiomeric excess (<i>ee</i>). Here we report that some small prochiral molecules exhibit <i>ee</i>-dependent splitting of ¹H NMR signals at room temperature based on acid/base interactions with chiral analytes, especially when either a chiral or prochiral acid contains a phenoxy group at the α-position of the carboxylic acid. As a representative case, the benzylamine (<b>BA</b>)/2-phenoxylpropionic acid (<b>PPA</b>) complex was comprehensively investigated by using various methods. Notably, X-ray crystallographic analysis shows that there are multipoint interactions in the <b>BA</b>/<b>PPA</b> complex, implying that “fixing” of molecular conformation is critical for efficient intermolecular transfer of magnetic anisotropy. Our results suggest that a wide range of prochiral molecules are available for NMR determination of <i>ee</i> when intermolecular interactions between prochiral molecules and chiral analytes are adequately designed

Chiral Guest Binding as a Probe of Macrocycle Dynamics and Tautomerism in a Conjugated Tetra­pyrrole

We report chiral guest binding as a probe of prototropic tautomerism and macrocyclic inversion in a highly conjugated tetra­pyrrole studied using ¹H NMR spectroscopy in conjunction with mandelic acid as the chiral guest. Both tautomerism and macrocycle inversion can be influenced in a non-trivial way depending on temperature and the respective concentrations of tetra­pyrrole host, chiral guest or water. Chirality of the interacting guest is the key feature since it permits separation and detailed observation of macrocyclic inversion and tautomerism. Based on this, a methodology was developed to identify and characterize the dynamic processes. Our observations suggest that yields of products (e.g., of asymmetric reactions) can be affected by reactivity of functional groups (in molecules undergoing tautomerism or inversion) by varying solution properties including reagent concentrations and impurities such as water. This work establishes a connection between the important chemical concepts of chirality, tautomerism, and macrocyclic dynamics

Chiral Guest Binding as a Probe of Macrocycle Dynamics and Tautomerism in a Conjugated Tetra­pyrrole

We report chiral guest binding as a probe of prototropic tautomerism and macrocyclic inversion in a highly conjugated tetra­pyrrole studied using ¹H NMR spectroscopy in conjunction with mandelic acid as the chiral guest. Both tautomerism and macrocycle inversion can be influenced in a non-trivial way depending on temperature and the respective concentrations of tetra­pyrrole host, chiral guest or water. Chirality of the interacting guest is the key feature since it permits separation and detailed observation of macrocyclic inversion and tautomerism. Based on this, a methodology was developed to identify and characterize the dynamic processes. Our observations suggest that yields of products (e.g., of asymmetric reactions) can be affected by reactivity of functional groups (in molecules undergoing tautomerism or inversion) by varying solution properties including reagent concentrations and impurities such as water. This work establishes a connection between the important chemical concepts of chirality, tautomerism, and macrocyclic dynamics

Chiral Guest Binding as a Probe of Macrocycle Dynamics and Tautomerism in a Conjugated Tetra­pyrrole

We report chiral guest binding as a probe of prototropic tautomerism and macrocyclic inversion in a highly conjugated tetra­pyrrole studied using ¹H NMR spectroscopy in conjunction with mandelic acid as the chiral guest. Both tautomerism and macrocycle inversion can be influenced in a non-trivial way depending on temperature and the respective concentrations of tetra­pyrrole host, chiral guest or water. Chirality of the interacting guest is the key feature since it permits separation and detailed observation of macrocyclic inversion and tautomerism. Based on this, a methodology was developed to identify and characterize the dynamic processes. Our observations suggest that yields of products (e.g., of asymmetric reactions) can be affected by reactivity of functional groups (in molecules undergoing tautomerism or inversion) by varying solution properties including reagent concentrations and impurities such as water. This work establishes a connection between the important chemical concepts of chirality, tautomerism, and macrocyclic dynamics

Thermo-/Mechano-Chromic Chiral Coordination Dimer: Formation of Switchable and Metastable Discrete Structure through Chiral Self-Sorting

Although strong chiral self-sorting often emerges in extended covalent or supramolecular polymers, the phenomenon is generally weak in discrete assemblies (e.g., dimers and oligomers) of small molecules due to the lack of a cooperative growth mechanism. Consequently, chiral self-sorting has been overlooked in the design of switchable and metastable discrete supramolecular structures. Here, we report a butyl-benzo[h]quinoline-based iridium(III) complex (Bu-Ir) with helical chirality at its metal center, which forms preferentially a homochiral dimer and exhibits thermo-/mechano-chromism based on a monomer–dimer transformation. While a five-coordinate monomer is formed in a racemic or an enantiopure Bu-Ir solution at 25 °C, a six-coordinate homochiral dimer complex is formed almost exclusively at low temperatures, with a higher degree of dimerization in enantiopure Bu-Ir solution. Estimation of apparent dimerization binding constants (K) and thermodynamic parameters (ΔH and ΔS) based on variable temperature ultraviolet–visible (UV–vis) and 1H NMR spectra reveals a strong preference for homochiral dimerization (largest known value for the coordination complex, Khomo/Khetero > 50). Notably, crystals of the homochiral dimer are metastable, undergoing a distinct color change upon grinding (from yellow to red) due to mechanical cleavage of coordination bonds (i.e., a dimer to monomer transformation). A comparison with control compounds having different substituents (proton, methyl, isopropyl, and phenyl groups) reveals that Bu-Ir dimerization involves both strong homochiral self-sorting preference and connected thermo-/mechano-chromic behavior, which is based on matched propeller-shaped chirality and subtle steric repulsion between alkyl substituents that render the homochiral dimer switchable and metastable. These findings provide substantial insights into the emergence of dynamic functionality based on the rational design of discrete chiral assemblies

Thermo-/Mechano-Chromic Chiral Coordination Dimer: Formation of Switchable and Metastable Discrete Structure through Chiral Self-Sorting

Although strong chiral self-sorting often emerges in extended covalent or supramolecular polymers, the phenomenon is generally weak in discrete assemblies (e.g., dimers and oligomers) of small molecules due to the lack of a cooperative growth mechanism. Consequently, chiral self-sorting has been overlooked in the design of switchable and metastable discrete supramolecular structures. Here, we report a butyl-benzo[h]quinoline-based iridium(III) complex (Bu-Ir) with helical chirality at its metal center, which forms preferentially a homochiral dimer and exhibits thermo-/mechano-chromism based on a monomer–dimer transformation. While a five-coordinate monomer is formed in a racemic or an enantiopure Bu-Ir solution at 25 °C, a six-coordinate homochiral dimer complex is formed almost exclusively at low temperatures, with a higher degree of dimerization in enantiopure Bu-Ir solution. Estimation of apparent dimerization binding constants (K) and thermodynamic parameters (ΔH and ΔS) based on variable temperature ultraviolet–visible (UV–vis) and 1H NMR spectra reveals a strong preference for homochiral dimerization (largest known value for the coordination complex, Khomo/Khetero > 50). Notably, crystals of the homochiral dimer are metastable, undergoing a distinct color change upon grinding (from yellow to red) due to mechanical cleavage of coordination bonds (i.e., a dimer to monomer transformation). A comparison with control compounds having different substituents (proton, methyl, isopropyl, and phenyl groups) reveals that Bu-Ir dimerization involves both strong homochiral self-sorting preference and connected thermo-/mechano-chromic behavior, which is based on matched propeller-shaped chirality and subtle steric repulsion between alkyl substituents that render the homochiral dimer switchable and metastable. These findings provide substantial insights into the emergence of dynamic functionality based on the rational design of discrete chiral assemblies

Thermo-/Mechano-Chromic Chiral Coordination Dimer: Formation of Switchable and Metastable Discrete Structure through Chiral Self-Sorting

Although strong chiral self-sorting often emerges in extended covalent or supramolecular polymers, the phenomenon is generally weak in discrete assemblies (e.g., dimers and oligomers) of small molecules due to the lack of a cooperative growth mechanism. Consequently, chiral self-sorting has been overlooked in the design of switchable and metastable discrete supramolecular structures. Here, we report a butyl-benzo[h]quinoline-based iridium(III) complex (Bu-Ir) with helical chirality at its metal center, which forms preferentially a homochiral dimer and exhibits thermo-/mechano-chromism based on a monomer–dimer transformation. While a five-coordinate monomer is formed in a racemic or an enantiopure Bu-Ir solution at 25 °C, a six-coordinate homochiral dimer complex is formed almost exclusively at low temperatures, with a higher degree of dimerization in enantiopure Bu-Ir solution. Estimation of apparent dimerization binding constants (K) and thermodynamic parameters (ΔH and ΔS) based on variable temperature ultraviolet–visible (UV–vis) and 1H NMR spectra reveals a strong preference for homochiral dimerization (largest known value for the coordination complex, Khomo/Khetero > 50). Notably, crystals of the homochiral dimer are metastable, undergoing a distinct color change upon grinding (from yellow to red) due to mechanical cleavage of coordination bonds (i.e., a dimer to monomer transformation). A comparison with control compounds having different substituents (proton, methyl, isopropyl, and phenyl groups) reveals that Bu-Ir dimerization involves both strong homochiral self-sorting preference and connected thermo-/mechano-chromic behavior, which is based on matched propeller-shaped chirality and subtle steric repulsion between alkyl substituents that render the homochiral dimer switchable and metastable. These findings provide substantial insights into the emergence of dynamic functionality based on the rational design of discrete chiral assemblies

Thermo-/Mechano-Chromic Chiral Coordination Dimer: Formation of Switchable and Metastable Discrete Structure through Chiral Self-Sorting

Although strong chiral self-sorting often emerges in extended covalent or supramolecular polymers, the phenomenon is generally weak in discrete assemblies (e.g., dimers and oligomers) of small molecules due to the lack of a cooperative growth mechanism. Consequently, chiral self-sorting has been overlooked in the design of switchable and metastable discrete supramolecular structures. Here, we report a butyl-benzo[h]quinoline-based iridium(III) complex (Bu-Ir) with helical chirality at its metal center, which forms preferentially a homochiral dimer and exhibits thermo-/mechano-chromism based on a monomer–dimer transformation. While a five-coordinate monomer is formed in a racemic or an enantiopure Bu-Ir solution at 25 °C, a six-coordinate homochiral dimer complex is formed almost exclusively at low temperatures, with a higher degree of dimerization in enantiopure Bu-Ir solution. Estimation of apparent dimerization binding constants (K) and thermodynamic parameters (ΔH and ΔS) based on variable temperature ultraviolet–visible (UV–vis) and 1H NMR spectra reveals a strong preference for homochiral dimerization (largest known value for the coordination complex, Khomo/Khetero > 50). Notably, crystals of the homochiral dimer are metastable, undergoing a distinct color change upon grinding (from yellow to red) due to mechanical cleavage of coordination bonds (i.e., a dimer to monomer transformation). A comparison with control compounds having different substituents (proton, methyl, isopropyl, and phenyl groups) reveals that Bu-Ir dimerization involves both strong homochiral self-sorting preference and connected thermo-/mechano-chromic behavior, which is based on matched propeller-shaped chirality and subtle steric repulsion between alkyl substituents that render the homochiral dimer switchable and metastable. These findings provide substantial insights into the emergence of dynamic functionality based on the rational design of discrete chiral assemblies