Host-guest interaction aided Zinc carry and delivery by ESIPT active 2-(2'-hydroxyphenyl)benzoxazole.

The effect of solvents and supramolecular hosts on the binding of metal ion with an excited state intramolecular proton transfer (ESIPT) active fluorophore 2-(2'-hydroxyphenyl)benzoxazole (HPBO) are investigated to scrutinize a possible metal ion carry and delivery system. The fluorophore forms strong fluorescent complex with Zn2+ ion. In aqueous medium, ß-cyclodextrin (ß-CD) breaks the HPBO-Zn2+ complex and encapsulate the freed fluorophore. Hence, the initially blocked ESIPT process is restored by forming an inclusion complex with the host molecules. However, in dimethyl sulphoxide (DMSO), ß-CD does not break the complex. But cucurbit[7]uril (CB-7) breaks the complex in both DMSO and water. The tuned emission characteristics are considered for constructing different molecular logic gates. BUFFER, NOT, PASS, IMPLICATION and INHIBIT logic operations are substantiated based on Zn2+, CB-7 and ß-CD response.

Modifying the proton transfer of 3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazole by water, confinement and confined water.

The effect of water, confinement and confined water on the proton transfer of 3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazole (bis-HPTA) was investigated. Water alters the proton transfer process. At higher pH, an anion is formed in water and it undergoes intermolecular proton transfer and forms a keto tautomer. Confinement of molecule in ß-cyclodextrin affects the intramolecular proton transfer. It also prevents the intermolecular proton transfer of the anionic form. In reverse micelle, the molecule resides in the interfacial region and interacts with bound water. The intermolecular hydrogen bond of the surfactants opens the intramolecular hydrogen bond in the weaker ß-ring of bis-HPTA. It led to single tautomer emission from bis-HPTA. An increase in water amount enhances the relative amount of trans-enol, but predominantly tautomer emission is observed.

Nanoparticle and surfactant controlled switching between proton transfer and charge transfer reaction coordinates.

The reaction coordinates of a molecular photo-switch 2-(4'-diethylamino-2'-hydroxyphenyl)-1H-imidazo-[4,5-b]pyridine (DHP) was tuned with a nanoparticle and surfactant. DHP undergoes excited state intramolecular proton transfer (ESIPT) and emits normal and tautomer emissions in N,N-dimethylformamide. Silver nanoparticles suppress the ESIPT and induce twisted intramolecular charge transfer (TICT). Further addition of surfactants alters the process. Interestingly, different surfactants cause different effects. Accordingly, the luminescence characteristics are altered. The anionic surfactant sodium dodecyl sulfate (SDS) restores the ESIPT process by completely detaching the molecule from the nanoparticle. The nonionic surfactant Triton X-100 (TX-100), at lower concentration, enhances the TICT emission and the ESIPT process is also observed due to the release of some fluorophore from the nanoparticle complex. But at higher concentration the fluorophores are released completely and the ESIPT process is restored. The cationic surfactant cetyltrimethyl ammonium bromide (CTAB), at lower concentration, simply restores the ESIPT process by releasing the fluorophore. But at higher CTAB concentration, DHP enters the metalparticle-CTAB aggregate and shows enhanced ESIPT.

Light-Driven Switching between Intramolecular Proton-Transfer and Charge-Transfer States.

A molecular photoswitch, 2-(4'-diethylamino-2'-hydroxyphenyl)-1H-imidazo-[4,5-b]pyridine (DHP), with mutually independent paths of excited-state intramolecular proton transfer (ESIPT) and twisted intramolecular charge transfer (TICT) was developed. Control over these processes was attained by switching the solvents. Depending on the solvent's hydrogen-bond capacity and polarity, either one of the photoprocesses (ESIPT or TICT) or both can be triggered. Accordingly, normal and tautomer emissions, normal and TICT emissions, or triple emission of normal, tautomer, and TICT were obtained from the molecule. The emissions were resolved by fluorescence lifetime. The conclusions were established by synthesizing and studying the methoxy derivative of the molecule.