Václav Březina

Rate of rotation of substituents in a molecular single stator-double rotor based on an oxidized resorcinarene with unsaturated hemiquinonoid groups at its meso positions ( i.e. , a fuchsonarene) has been controlled according to solvent polarity and acidity.

NMR spectroscopy cannot be used to discriminate enantiomers, and NMR resonances of enantiomeric mixtures are generally not affected by enantiomeric excess (ee). Here we report that a coordination complex (L·2Zn·3C), where L is a salen-like prochiral ligand and C is an exchangeable acetate co-ligand, exhibits symmetrical splitting of one of the 1H-NMR resonances of L with the degree of splitting linearly proportional to ee of the chiral guest co-ligand C, 2-phenoxypropionic acid (PPA). Despite the well-defined chirality in the crystal structure of L·2Zn·3C, concurrent fast chiral inversion and co-ligand exchange in solution renders L·2Zn·3C the primary example of prochiral solvating agent (pro-CSA) based on a coordination complex. Notably, the NMR resonances remain split even in dilute solution due to the lack of chiral guest dissociation in the co-ligand exchange system. This work provides new insights into chiral transfer events in metal-ligand complexes.

Interactions of anionic guests with a tritopic peripherally functionalized conjugated calix[4]pyrrole host (1) prepared using a regioselective synthetic method is reported. The regioselectivity of synthesis relies on selective N-alkylation of the calix[4]pyrrole caused by peripheral substitution of one pyrrole group with subsequent N-alkylation at the opposing pyrrole group termed by us ‘knock-on’ regioselectivity. The resulting host molecule exhibits anion interactions with common chloride and nitrate anions enhanced by an order of magnitude over the parent conjugated calix[4]pyrrole. Combined analysis of ¹H NMR and UV-vis spectroscopic titration data enabled an evaluation of binding strengths of anions with the host K_A in a binding model where the salt dissociation process is also incorporated in the form of its dissociation constant K_d. Anions could be classified as two types based on their interactions with 1: Type A anions (chloride, nitrate, perchlorate, hydrogensulphate) associate as 1 : 1 complexes through hydrogen bonding while interactions involving Type B anions (acetate, fluoride, dihydrogenphosphate) are complicated by host deprotonation and/or countercation association. Hosts based on rim-functionalized calix[4]pyrroles such as 1 represent a promising new family of chromophores for estimation of biologically relevant anions or other species.

Poly(N-isopropylacrylamide) (PNIPAM) is an important polymer with stimuli-responsive properties, making it suitable for various uses. Phase behavior of the temperature-sensitive PNIPAM polymer in the presence of four low-molecular weight additives tert-butylamine (t-BuAM), tert-butyl alcohol (t-BuOH), tert-butyl methyl ether (t-BuME), and tert-butyl methyl ketone (t-BuMK) was studied in water (D₂O) using high-resolution nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering. Phase separation was thermodynamically modeled as a two-state process which resulted in a simple curve which can be used for fitting of NMR data and obtaining all important thermodynamic parameters using simple formulas presented in this paper. The model is based on a modified van’t Hoff equation. Phase separation temperatures T_p and thermodynamic parameters (enthalpy and entropy change) connected with the phase separation of PNIPAM were obtained using this method. It was determined that T_p is dependent on additives in the following order: T_p(t-BuAM) > T_p(t-BuOH) > T_p(t-BuME) > T_p(t-BuMK). Also, either increasing the additive concentration or increasing pK_a of the additive leads to depression of T_p. Time-resolved ¹H NMR spin–spin relaxation experiments (T₂) performed above the phase separation temperature of PNIPAM revealed high colloidal stability of the phase-separated polymer induced by the additives (relative to the neat PNIPAM/D₂O system). Small quantities of selected suitable additives can be used to optimize the properties of PNIPAM preparations including their phase separation temperatures, colloidal stabilities, and morphologies, thus improving the prospects for the application.

Herein, we modulate the chromic response of a highly colored tetrapyrrole macrocycle, namely, tetrakis(3,5‐di‐tert‐butyl‐4‐oxocyclohexadien‐2,5‐yl)porphyrinogen (OxP) by structural modification. N‐Benzylation at the macrocyclic nitrogen atoms leads to stepwise elimination of the two calix[4]pyrrole‐type binding sites of OxP and serial variation of the chromic properties of the products, double N‐benzylated Bz₂OxP and tetra N‐benzylated Bz₄OxP. The halochromic (response to acidity) and solvatochromic (response to solvent polarity) properties were studied by using UV/Vis spectroscopy and NMR spectroscopy in nonpolar organic solvents. Titration experiments were used to generate binding isotherms to elucidate their binding properties with difluoroacetic acid. Differences in the halochromic properties of the compounds allowed construction of a colorimetric scale of acidity in nonpolar solvents, as the compounds in the series OxP, Bz₂OxP, and Bz₄OxP are increasingly difficult to protonate but maintain their propensity to change color upon protonation. The concurrent effects of binding‐site blocking and modulation of acidity sensitivity are important new aspects for the development of colorimetric indicators.