Metal binding pattern of acyclovir in ternary copper(II) complexes having an S-thioether or S-disulfide NO2S-tripodal tetradentate chelator

González‐Pérez, Josefa María; Choquesillo-Lazarte, Duane; Domínguez‐Martín, Alicia; Vílchez-Rodríguez, Esther; Pérez-Toro, Inmaculada; Castiñeiras, Alfonso; Arriortua, Oihane; García-Rubiño, María Eugenia; Matilla, Ángel J.; Niclós‐Gutiérrez, Juan

doi:10.1016/j.ica.2016.05.005

Cited by 10 publications

(14 citation statements)

References 32 publications

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“…A terminally bonded t Bu 2 S on each copper center (CeÀ S = 2.479(2) Å) then completes a 5-coordinate environment for them, if a week Cu…Cu interaction (3.039(2) Å) is not taken into account. While the CuÀ O bond distances compare well with the literature, [45] the CuÀ S distance in 1 is actually shorter than those reported for related Cu(II) thioether complexes, [46] indicating that t Bu 2 S is strongly coordinated to copper center. The silver analogue [Ag 4 (μ 3 ,η 1 ,η 2 -TFA) 2 (μ,η 1 ,η 1 -TFA) 2 (μ,η 1 ,η 1 -t Bu 2 S)(η 1 -t Bu 2 S) 3 ] (2), on the other hand, shows a zigzag tetranuclear structure constructed with the help of two triply bridging μ 3 ,η 1 ,η 2 -TFA, two doubly bridging μ,η 1 ,η 1 -TFA and one doubly bridging μ,η 1 ,η 1 -t Bu 2 S ligands.…”

supporting

confidence: 82%

Coinage Metal Complexes with Di‐tertiary‐butyl Sulfide as Precursors with Ultra‐Low Decomposition Temperature

Gahlot

Purohit

Jeanneau

et al. 2021

Chemistry A European J

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We report here the synthesis of [Cu 2 (TFA) 4 ( t Bu 2 S) 2 ] (1), [Ag 4 (TFA) 4 ( t Bu 2 S) 4 ] (2) and [AuCl( t Bu 2 S)] (3) (TFA = trifluoroacetate), which decompose in solution medium at ultra-low temperature (e. g., in boiling toluene) to afford phase-pure and highly crystalline Cu 9 S 5 , Ag 2 S and metallic Au nanoparticles, respectively. The low decomposition temperature of these precursors is attributed to the facile decomposition mechanism in the di-tertiary-butyl sulfide ligand. These results are a significant step in the direction of establishing a general low-temperature strategy spanning a range of systems including thermodynamically metastable materials and incorporate them in technologies that are sensitive to the harsh conditions.

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supporting

confidence: 82%

Coinage Metal Complexes with Di‐tertiary‐butyl Sulfide as Precursors with Ultra‐Low Decomposition Temperature

Gahlot

Purohit

Jeanneau

et al. 2021

Chemistry A European J

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“…Along the past decades, mainly three research groups have contributed to enlighten the metal binding abilities of acyclovir [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ]. According to this information, acv preferentially acts as monodentate ligand, involving the purine moiety, with the M-N7(acv) coordination bond acting in cooperation with an intramolecular interligand D-H···O6(acv) interaction (D = oxygen or nitrogen H-donor atoms) [ 8 , 10 , 11 , 13 , 16 , 18 , 19 , 20 , 21 , 22 ]. Besides this preferred molecular recognition pattern, further studies have reported more unconventional modes for acv such as the N7,O6-chelating mode or even the tetradentate μ 3 -N7,O6,O(e),O(ol) mode [ 12 , 14 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

Deciphering the H-Bonding Preference on Nucleoside Molecular Recognition through Model Copper(II) Compounds

et al. 2021

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The synthetic nucleoside acyclovir is considered an outstanding model of the natural nucleoside guanosine. With the purpose of deepening on the influence and nature of non-covalent interactions regarding molecular recognition patterns, three novel Cu(II) complexes, involving acyclovir (acv) and the ligand receptor N-(2-hydroxyethyl)ethylenediamine (hen), have been synthesized and thoroughly characterized. The three novel compounds introduce none, one or two acyclovir molecules, respectively. Molecular recognition has been evaluated using single crystal X-ray diffraction. Furthermore, theoretical calculations and other physical methods such as thermogravimetric analysis, infrared and UV-Vis spectroscopy, electron paramagnetic resonance and magnetic measurements have been used. Theoretical calculations are in line with experimental results, supporting the relevance of the [metal-N7(acv) + H-bond] molecular recognition pattern. It was also shown that (hen)O-H group is used as preferred H-donor when it is found within the basal coordination plane, since the higher polarity of the terminal (hen)O-H versus the N-H group favours its implication. Otherwise, when (hen)O-H occupies the distal coordination site, (hen)N-H groups can take over.

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“…33 For Cu(II)disulfide bonds in axial coordination the span of covered Cu-S bond lengths is 2.68 Å to 3.28 Å in ref. [62][63][64][65][66]. For a Cu(II)disulfide linkage with a rare case of seemingly equal six Cu-ligand bonds 67 Cu-S is within 2.46-2.57 Å, which is longer than that characteristic of Cu(I)-disulfide.…”

Section: Dft Calculationsmentioning

confidence: 94%

Structural dynamics upon photoexcitation-induced charge transfer in a dicopper(i)–disulfide complex

Naumova

Khakhulin

Rębarz

et al. 2018

Phys. Chem. Chem. Phys.

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The structural dynamics of charge-transfer states of nitrogen-ligated copper complexes has been extensively investigated in recent years following the development of pump-probe X-ray techniques. In this study we extend this approach towards copper complexes with sulfur coordination and investigate the influence of charge transfer states on the structure of a dicopper(i) complex with coordination by bridging disulfide ligands and additionally tetramethylguanidine units [Cu(NSSN)]. In order to directly observe and refine the photoinduced structural changes in the solvated complex we applied picosecond pump-probe X-ray absorption spectroscopy (XAS) and wide-angle X-ray scattering (WAXS). Additionally, the ultrafast evolution of the electronic excited states was monitored by femtosecond transient absorption spectroscopy in the UV-Vis probe range. DFT calculations were used to predict molecular geometries and electronic structures of the ground and metal-to-ligand charge transfer states with singlet and triplet spin multiplicities, i.e. S, MLCT andMLCT, respectively. Combining these techniques we elucidate the electronic and structural dynamics of the solvated complex upon photoexcitation to the MLCT states. In particular, femtosecond optical transient spectroscopy reveals three distinct timescales of 650 fs, 10 ps and >100 ps, which were assigned as internal conversion to the ground state (S → S), intersystem crossing MLCT →MLCT, and subsequent relaxation of the triplet to the ground state, respectively. Experimental data collected using both X-ray techniques are in agreement with the DFT-predicted structure for the triplet state, where coordination bond lengths change and one of the S-S bridges is cleaved, causing the movement of two halves of the molecule relative to each other. Extended X-ray absorption fine structure spectroscopy resolves changes in Cu-ligand bond lengths with precision on the order of 0.01 Å, whereas WAXS is sensitive to changes in the global shape related to relative movement of parts of the molecule. The results presented herein widen the knowledge on the electronic and structural dynamics of photoexcited copper-sulfur complexes and demonstrate the potential of combining the pump-probe X-ray absorption and scattering for studies on photoinduced structural dynamics in copper-based coordination complexes.

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Metal binding pattern of acyclovir in ternary copper(II) complexes having an S-thioether or S-disulfide NO2S-tripodal tetradentate chelator

Cited by 10 publications

References 32 publications

Coinage Metal Complexes with Di‐tertiary‐butyl Sulfide as Precursors with Ultra‐Low Decomposition Temperature

Coinage Metal Complexes with Di‐tertiary‐butyl Sulfide as Precursors with Ultra‐Low Decomposition Temperature

Deciphering the H-Bonding Preference on Nucleoside Molecular Recognition through Model Copper(II) Compounds

Structural dynamics upon photoexcitation-induced charge transfer in a dicopper(i)–disulfide complex

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