OH⋯S intramolecular hydrogen bond in thiomalonaldehyde derivatives; a quantum chemical study

Nowroozi, Alireza; Roohi, Hossein; Hajiabadi, H.; Raissi, Heidar; Khalilinia, Ebrahim; Birgan, M. Najafi

doi:10.1016/j.comptc.2010.11.029

Cited by 18 publications

(7 citation statements)

References 28 publications

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“…For example, some previous reports have evidenced that the methionine-containing dipeptides can form amideNH···S H-bonds that are even stronger than amideNH···OC H-bonds. , In artificial DNA or RNA researches, sulfur H-bonds have been popularly applied in RNAi resistant genes and protein engineering . Moreover, recent high-resolution spectroscopy in combination with quantum chemical calculations has revealed that sulfur-containing H-bonds can be as strong as conventional H-bonds. − …”

Section: Introductionmentioning

confidence: 99%

Chapter Open for the Excited-State Intramolecular Thiol Proton Transfer in the Room-Temperature Solution

et al. 2021

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We report here, for the first time, the experimental observation on the excited-state intramolecular proton transfer (ESIPT) reaction of the thiol proton in room-temperature solution. This phenomenon is demonstrated by a derivative of 3-thiolflavone (3TF), namely, 2-(4-(diethylamino)phenyl)-3mercapto-4H-chromen-4-one (3NTF), which possesses an SH•••O intramolecular H-bond (denoted by the dashed line) and has an S 1 absorption at 383 nm. Upon photoexcitation, 3NTF exhibits a distinctly red emission maximized at 710 nm in cyclohexane with an anomalously large Stokes shift of 12 230 cm −1 . Upon methylation on the thiol group, 3MeNTF, lacking the thiol proton, exhibits a normal Stokes-shifted emission at 472 nm. These, in combination with the computational approaches, lead to the conclusion of thiol-type ESIPT unambiguously. Further time-resolved study renders an unresolvable (<180 fs) ESIPT rate for 3NTF, followed by a tautomer emission lifetime of 120 ps. In sharp contrast to 3NTF, both 3TF and 3-mercapto-2-(4-(trifluoromethyl)phenyl)-4Hchromen-4-one (3FTF) are non-emissive. Detailed computational approaches indicate that all studied thiols undergo thermally favorable ESIPT. However, once forming the proton-transferred tautomer, the lone-pair electrons on the sulfur atom brings nonnegligible nπ* contribution to the S 1 ′ state (prime indicates the proton-transferred tautomer), for which the relaxation is dominated by the non-radiative deactivation. For 3NTF, the extension of π-electron delocalization by the diethylamino electron-donating group endows the S 1 ′ state primarily in the ππ* configuration, exhibiting the prominent tautomer emission. The results open a new chapter in the field of ESIPT, covering the non-canonical sulfur intramolecular H-bond and its associated ESIPT at ambient temperature.

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Section: Introductionmentioning

confidence: 99%

Chapter Open for the Excited-State Intramolecular Thiol Proton Transfer in the Room-Temperature Solution

et al. 2021

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“…There have been interesting but few reports on H-bonds that involve a sulfur atom as either the proton donor (S–H) or acceptor (S). The concept of “sulfur participating in an H-bond” appeared in early reports despite the relatively low electronegativity (2.58) for sulfur on the Pauling scale. − Recent quantum chemical calculations in conjunction with high-resolution spectroscopic evidence have revealed that sulfur-containing H-bond can be as strong as conventional H-bonds. − In biological systems, methionine-containing dipeptides have been reported to form amide-N–H···S intermolecular H-bonds that are stronger than amide-N–H···OC H-bonds . Additionally, the strengths of the intermolecular H-bonds in thiobase pairs are reported to be of the same magnitude with the canonical nucleobase pairs .…”

Section: Introductionmentioning

confidence: 99%

Sulfur-Based Intramolecular Hydrogen-Bond: Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence

Liu

Huang

et al. 2019

J. Am. Chem. Soc.

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We report O−H----S hydrogen-bond (Hbond) formation and its excited-state intramolecular H-bond on/off reaction unveiled by room-temperature phosphorescence (RTP). In this seminal work, this phenomenon is demonstrated with 7-hydroxy-2,2-dimethyl-2,3-dihydro-1Hindene-1-thione (DM-7HIT), which possesses a strong polar (hydroxy)-dispersive (thione) type H-bond. Upon excitation, DM-7HIT exhibits anomalous dual RTP with maxima at 550 and 685 nm. This study found that the lowest lying excited state (S 1 ) of DM-7HIT is a sulfur nonbonding (n) to π* transition, which undergoes O−H bond flipping from S 1 (nπ*) to the non-H-bonded S′ 1 (nπ*) state, followed by intersystem crossing and internal conversion to populate the T′ 1 (nπ*) state. Fast H-bond on/off switching then takes place between T′ 1 (nπ*) and T 1 (nπ*), forming a pre-equilibrium that affords both the T′ 1 (nπ*, 685 nm) and T 1 (nπ*, 550 nm) RTP. The generality of the sulfur H-bond on/off switching mechanism, dubbed a molecule wiper, was rigorously evaluated with a variety of other H-bonded thiones, and these results open a new chapter in the chemistry of hydrogen bonds.

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“…According to the previous studies, some of the topological parameters of HB critical point and ring critical point, especially electron charge density, are well correlated with IMHB energy [34,35]. Hence, we first considered the charge density for the evaluation of the IMHB strength in all of the title compounds.…”

Section: Topological Descriptorsmentioning

confidence: 99%

A comparative study of two-ring resonance-assisted hydrogen bond systems

et al. 2015

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Two-ring resonance-assisted hydrogen bond (RAHB) systems can be obtained by merging two cis enol ring of malondialdehyde with different orientations. In the present work, a comparative theoretical study of all of the possible two-ring RAHB systems, 2,3-dihydroxy-2-butene-4-dial (DBD), 1,5-dihydroxy-1,4-diene-3-pentanone (DDP) and 2-dihydroxy-methylene-propanediol (DMP), was carried out. Also, the influence of the co-existence of two RAHB rings on the molecular structures, intramolecular hydrogen bond (IMHB) and the p-electron delocalization (p-ED) was investigated. In this regard, ab initio calculations on the various equilibrium conformations of DBD, DDP and DMP at MP2/6-311??G(d,p) level of theory have been performed and the IMHB strength of model compounds by different descriptors such as geometrical, topological, molecular orbital, spectroscopic and energetic parameters was evaluated. Then, the p-ED of DBD, DDP and DMP was estimated by using a variety of indicators, such as geometrical factor of Gilli (k), the harmonic oscillator model of aromaticity, the nucleus-independent chemical shift, the para delocalization index, the average two-center index, the aromatic fluctuation index. Finally, based on the computational results, it was found that the strength of IMHB and significance of p-ED in two-ring RAHB systems are strongly related to the relative flow of p-electrons in two rings. In other words, the parallel flows of p-electrons in DMP and DDP increase the IMHB strength and p-ED, while opposite flow of p-electrons in DBD decreases the IMHB strength and p-ED.

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OH⋯S intramolecular hydrogen bond in thiomalonaldehyde derivatives; a quantum chemical study

Cited by 18 publications

References 28 publications

Chapter Open for the Excited-State Intramolecular Thiol Proton Transfer in the Room-Temperature Solution

Chapter Open for the Excited-State Intramolecular Thiol Proton Transfer in the Room-Temperature Solution

Sulfur-Based Intramolecular Hydrogen-Bond: Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence

A comparative study of two-ring resonance-assisted hydrogen bond systems

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