Abstract The tautomeric equilibrium of sildenafil molecule was theoretically studied using B3LYP and M06-2X density functional theory (DFT) methods in connection with aug-cc-pVDZ correlation consistent basis set. Calculations were performed for gas phase water solution conditions modelled by polarizable continuum model (PCM). Three forms are possible. Two keto forms: A — where the proton more d...

The title hydrated molecular salt, C(12)H(9)N(2)OS(+)·Br(-)·H(2)O, the aza-substituted six-membered ring is present as its keto tautomer instead of its aromatic tautomer. The dihedral angle between the fused ring system and the pyridinone ring in the cation is 6.91 (6)°. In the crystal, bifurcated N-H⋯(O,Br) and O-H⋯Br hydrogen bonds and S⋯O contacts [S⋯O = 3.0526 (10) Å] connect the components...

The effect of tautomerism on the mismatch discrimination was studied on 7-deazapurine and 8-aza-7-deazapurine analogues of isoguanosine. 7-Halogenated 7-deaza-2'-deoxyisoguanosines show better base pair discrimination than 2'-deoxyisoguanosine due to the more favored keto tautomer formation. 8-Aza-7-deazaisoguanosine and its 7-halogeno derivatives also show higher keto tautomer population than ...

A new cobalt bis(semiquinone) valence tautomer is reported featuring a terthienyl substituent, which undergoes electropolymerization to produce a valence tautomeric conducting metallopolymer.

A comprehensive picture of the ultrafast nonradiative decay mechanisms of three cytosine tautomers (amino-keto, imino-keto, and amino-enol forms) is revealed by high-level ab initio potential energy calculations using the multistate (MS) CASPT2 method and also by on-the-fly excited-state molecular dynamics simulations employing the CASSCF method. To obtain a reliable potential energy profile al...

2,5-Diamino-1,4-benzoquinonediimine (DABQDI) derivatives possessing two electron-withdrawing aromatic N-substituents can potentially exhibit a zwitterionic ground state in lieu of the expected canonical structure. It was previously shown that use nitroaromatics groups (EWG) could yield quantitative formation tautomer DABQDI polar solvents, while mixture and forms present low polarity solvents. ...

In order to study the effect of halogen bond on tautomerism in β-diketones solid-state, we have prepared a series cocrystals derived from an asymmetric β-diketone, benzoyl-4-pyridoylmethane (b4pm), as acceptor and perfluorinated iodobenzenes: iodopentaflourobenzene (ipfb), 1,2-, 1,3- 1,4-diiodotetraflorobenzene (12tfib, 13tfib 14tfib) 1,3,5-triiodo-2,4,6-trifluorobenzene (135titfb). All five ar...

An algorithm is introduced that enables a fast generation of all possible prototropic tautomers resulting from the mobile H atoms and associated heteroatoms as defined in the InChI code. The InChI-derived set of possible tautomers comprises (1,3)-shifts for open-chain molecules and (1,n)-shifts (with n being an odd number >3) for ring systems. In addition, our algorithm includes also, as extens...

We investigated spectral holes burnt at 1.5 K into the origins of several tautomeric forms of mesoporphyrin IX-substituted horseradish peroxidase at pH 8 under pressures up to 2 MPa. From the pressure-induced lineshift the compressibility of the apoprotein could be determined. We found that the compressibility changed significantly when measured at different tautomer origins. It was concluded t...