A distinction between the S-cis and S-trans conformations of planar dithiooxamides with infrared spectroscopy

Slootmaekers, B.; Perlepes, S. P.; Desseyn, H. O.

doi:10.1016/0584-8539(95)01558-2

Cited by 7 publications

(7 citation statements)

References 10 publications

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“…[34] In the cis conformation, the steric hindrance between the hydrogens shifts the inplane NH 2 deformation modes to higher frequencies, compared with the trans one. [35][36][37] The CN stretching modes are coupled to the NH 2 deformation, thus ν-CN is also shifted to higher frequencies in the cis species, in agreement with the theoretical Raman calculations. In both conformations, the CN and CS bending modes can also be coupled and the shifts on S-CN and NH 2 frequency modes can be used to differentiate both species.…”

Section: Spectroscopic and Theoretical Studies Of The Free Dto Moleculesupporting

confidence: 85%

“…NH 2 very characteristic of the region. [37][38][39] After a few minutes, the intensity of the 683 cm −1 band decreases as expected, due to the nature of the vibration, more intense for the cis species. Another prominent difference is the relative intensity of 965 cm −1 with 3 min and the abrupt inversion with the 932 cm −1 band, both assigned to δ sy.…”

Section: Spectroscopic and Theoretical Studies Of The Free Dto Moleculesupporting

confidence: 75%

“…C‐C + δ asy.op.oph. NH 2 very characteristic of the region . After a few minutes, the intensity of the 683 cm −1 band decreases as expected, due to the nature of the vibration, more intense for the cis species.…”

Section: Resultsmentioning

confidence: 99%

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Probing the dynamics of dithiooxamide coordinated to gold nanoparticles using SERS

Grasseschi

Zamarion

Toma

2018

J Raman Spectroscopy

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The substitution kinetics and specific binding modes of the dithiooxamide (dto) ligand at the metal surface have been investigated and interpreted on the light of theoretical and experimental Raman studies. By monitoring the vibrational properties of this ligand, it was shown that gold nanoparticles employed as surface‐enhanced effects (SERS) probes are strongly dependent on the coordination chemistry of the ligands at the metal interface. The binding of dto to the gold nanoparticles led to linkage isomers, and at low concentrations, the bidentate form, corresponding to bis‐thione‐Au bond in cis configuration {Au‐S(NH2)CC(NH2)S‐Au}, was the predominating species. Even at high concentrations, the cis‐configuration was observed first; but as the ligand competition dynamics proceeded, the binding mode gradually changed into a monodentate thione‐Au mode {AuS(NH2)CCS(NH2)}. In this mode, the dto ligand adopts a thermodynamically favorable trans‐conformation geometry, producing dramatic changes in the SERS spectra. Such dynamic behavior of the ligand at the metal plasmonic surface is of crucial importance, as one of the possible factors associated with lack of reproducibility of the SERS spectra frequently reported in the literature.

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Section: Spectroscopic and Theoretical Studies Of The Free Dto Moleculesupporting

confidence: 85%

Section: Spectroscopic and Theoretical Studies Of The Free Dto Moleculesupporting

confidence: 75%

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Probing the dynamics of dithiooxamide coordinated to gold nanoparticles using SERS

Grasseschi

Zamarion

Toma

2018

J Raman Spectroscopy

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“…This is consistent with the symmetry reduced from Td for the unperturbated clod-ions to CsV for the monodentate perchlorato ligands [38,41]. This discrepancy has also been recently [19] observed in the IR spectra of Assignments of the far-IR metal-ligand stretching bands have been carefully made by noting (i) the frequencies of the internal modes of the free ligand HL, (ii) bands principally dependent on X (X = CI, Br, I, NCS, SCN), (iii) the variation in band position with deuteration, and (iv) extensive literature reports [4,[6][7][8][9][10][11][12][13][14][16][17][18][19][20][21][22]38,43]. aln general, satisfactory Raman spectra could not be obtained because the complexes are highly fluorescent in the laser beam.…”

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confidence: 99%

Synthesis, Physical Properties and Spectroscopy of Pd(II) Complexes With CH₃OOCCSNH₂

Jacobs¹,

Dimitrou

Perlepes

et al. 1989

Bulletin des Soc Chimique

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ABSTRACTstudies. The vibrational analysis of the complexes is also given using deuterium isolopic substitutions. Monomeric square planar structures are assigned for the 1 :2 and 1 :4 complexes in the solid state ; the 1 :1 nitrato complex is a polymer containing both monodentate and bidentate bridging nitrato groups. The thioamide sulfur atom of HL is the donor atom to Pd(ll) and pt(ll).The thiocyanate ions are coordinated through sulfur in the trans complex and through nitrogen in the cis product. This differentiation in the mode of thiocyanate bonding is discussed.

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“…Já na forma trans não há esse impedimento e esses modos se encontram deslocados para valores de frequências menores. [252][253][254] Vibrações de deformação NH2 no plano possuem um acoplamento com modos de estiramento CN, assim sendo esses modos devem ser encontrados em frequências maiores quando a Dto encontra-se na forma cis.…”

Section: Figura 74: Geometria Otimizada (Esquerda) Homo (Meio) Lumounclassified

Uma abordagem fundamental sobre nanopartículas de ouro

Grasseschi¹

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O estudo sistemático de nanopartículas de ouro utilizando conceitos fundamentais de química de coordenação e físico-química é o foco principal desta tese, que trata principalmente da natureza das interações moleculares na superfície de nanopartículas. Para tal finalidade, estudou-se como as variações dos parâmetros experimentais influenciam no mecanismo de formação das partículas pelo "método de Turkevich". Observou-se que, não somente, a morfologia e as propriedades ópticas estão atreladas aos processos de nucleação e crescimento, mas também a composição e as propriedades químicas da camada molecular ao redor das partículas. Dessa forma, foi possível comprovar, teórica e experimentalmente, que um intermediário instável da reação de oxidação do citrato de sódio, a acetonadicarboxilato, se torna estável devido a coordenação aos átomos superficiais de ouro. Isto leva a propriedades químicas e espectroscópicas distintas, principalmente, frente a reações de troca de ligantes na superfície das partículas. Foi feito um estudo, teórico e experimental, sistemático das propriedades das moléculas de etanobis(tioamida) na superfície de diferentes nanopartículas de ouro, comprovando que a presença de acetonadicarboxilato, ao final da síntese das partículas, influencia drasticamente nas propriedades do sistema.

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A distinction between the S-cis and S-trans conformations of planar dithiooxamides with infrared spectroscopy

Cited by 7 publications

References 10 publications

Probing the dynamics of dithiooxamide coordinated to gold nanoparticles using SERS

Probing the dynamics of dithiooxamide coordinated to gold nanoparticles using SERS

Synthesis, Physical Properties and Spectroscopy of Pd(II) Complexes With CH₃OOCCSNH₂

Uma abordagem fundamental sobre nanopartículas de ouro

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A distinction between the S-cis and S-trans conformations of planar dithiooxamides with infrared spectroscopy

Cited by 7 publications

References 10 publications

Probing the dynamics of dithiooxamide coordinated to gold nanoparticles using SERS

Probing the dynamics of dithiooxamide coordinated to gold nanoparticles using SERS

Synthesis, Physical Properties and Spectroscopy of Pd(II) Complexes With CH3OOCCSNH2

Uma abordagem fundamental sobre nanopartículas de ouro

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Synthesis, Physical Properties and Spectroscopy of Pd(II) Complexes With CH₃OOCCSNH₂