The Se … Hal halogen bonding: Co-crystals of selenoureas with fluorinated organohalides

Chernysheva, Maria V.; Rautiainen, J. Mikko; Ding, Xin; Haukka, Matti

doi:10.1016/j.jssc.2020.121930

Cited by 4 publications

(8 citation statements)

References 74 publications

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“…The stabilities of the solid-state A and B XB structures likely stem from their ability to from continuous zigzag and linear XB chains, as already discussed in the crystal structure section above. It is noteworthy that the Δ E int for XB complexes of 7 are slightly weaker than Δ E int calculated recently at the same level of theory for B complexes of related selenocarbonyls SeC(NH 2 ) 2 and SeC(NH 2 )(NMe 2 ) (Δ E int = −32.8 and −36.8 kJ mol –1 , respectively) . The same trend has been observed also in other halogen-bonded systems containing sulfur and selenium acceptors. , …”

Section: Resultssupporting

confidence: 71%

“…It is noteworthy that the ΔE int for XB complexes of 7 are slightly weaker than ΔE int calculated recently at the same level of theory for B complexes of related selenocarbonyls SeC(NH 2 ) 2 and SeC(NH 2 )(NMe 2 ) (ΔE int = −32.8 and −36.8 kJ mol −1 , respectively). 61 The same trend has been observed also in other halogen-bonded systems containing sulfur and selenium acceptors. 14,62 In the case of the 2:1 and 4:1 donor/acceptor complexes, the optimized XB contacts become longer than the XB contacts observed in the crystal structure of 7A, supporting the suggestion that the overall packing of the molecules facilitates the formation of four halogen bonds from acceptor 7.…”

Section: ■ Experimental Sectionsupporting

confidence: 58%

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Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Happonen

Rautiainen

Valkonen

2021

Crystal Growth & Design

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The halogen bonding (XB) between 1,2-diiodotetrafluorobenzene (1,2-DITFB) or 1,4-diiodotetrafluorobenzene (1,4-DITFB) and the selection of different thiocarbonyl acceptors was studied by the single-crystal X-ray diffraction method. Diiodotetrafluorobenzenes (DITFBs) were found to form C-I···S halogen-bonded 1:1, 2:1, and 1:2 (donor/acceptor ratio) complexes with thiocarbonyls. Lengths of contacts were found to be clearly shorter than the sum of van der Waals radii of iodine and sulfur as well as the contact angles showed values close to linear, so the XB interactions could be verified. One sulfur atom showed the ability to accept one, two, or four XB interactions, and the acceptor angle can vary more than 35°. Solid-state packing of thiocarbonyl-XB complexes was found to be greatly affected by the size and type of the acceptor used. Halogen and hydrogen bonding cooperativity was found in some of the complexes if the used acceptor was suitable to form both bonds. Here, we present 19 new structures of these complexes, which can be rather easily prepared by mixing the components in the solutions and letting them crystallize in loosely sealed tubes. Computational analysis carried out for the XB complexes of N,N′-dimethylthiourea supported very closely the findings of the experimental study.

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Section: Resultssupporting

confidence: 71%

Section: ■ Experimental Sectionsupporting

confidence: 58%

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Happonen

Rautiainen

Valkonen

2021

Crystal Growth & Design

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“…The strength of the selenium-containing compound is not unprecedented as its analogue, Ph 3 PSe, was shown to exhibit significant XB interactions with diiodotetrafluorobenzene during crystallization studies . Other selenide and sulfide molecules have also been reported to form crystals through strong XB interactions with 1,4-diiodotetrafluorobenzene and 1,4-dibromotetrafluorobenzene . In the same study, Chernysheva and co-workers observed that selenium-containing XB acceptors appear to engage in stronger XB with XB donors than their sulfur-containing counterparts …”

Section: Resultsmentioning

confidence: 98%

“…74 Other selenide and sulfide molecules have also been reported to form crystals through strong XB interactions with 1,4-diiodotetrafluorobenzene and 1,4-dibromotetrafluorobenzene. 75 In the same study, Cherny-sheva and co-workers observed that selenium-containing XB acceptors appear to engage in stronger XB with XB donors than their sulfur-containing counterparts. 75 Another aspect of the data collected in this section is the ability to compare two systems varying only by the R group: Oct 3 PB: versus Ph 3 PB:.…”

Section: Dft and Nmr Analysis Of Xb Acceptorsr Groupmentioning

confidence: 93%

“…75 In the same study, Cherny-sheva and co-workers observed that selenium-containing XB acceptors appear to engage in stronger XB with XB donors than their sulfur-containing counterparts. 75 Another aspect of the data collected in this section is the ability to compare two systems varying only by the R group: Oct 3 PB: versus Ph 3 PB:. Experiments of IPFB with XB acceptors featuring the phenyl group with O, S, and Se as the Lewis-base atom show either lower K a values (3.82 M −1 for Ph 3 PO) or negligible changes of NMR chemical shifts during titrations for indefinite K a measurements (Table 2).…”

Section: Dft and Nmr Analysis Of Xb Acceptorsr Groupmentioning

confidence: 93%

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Evaluating Halogen-Bond Strength as a Function of Molecular Structure Using Nuclear Magnetic Resonance Spectroscopy and Computational Analysis

et al. 2021

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Halogen bonding (XB) is a highly directional, noncovalent intermolecular interaction between a molecule (XB donor) presenting a halogen with an electron-deficient region or sigma hole (σhole) and an electron-rich or Lewis-base molecule (XB acceptor). A systematic, experimental, and theoretical study of solution-phase XB strength as a function of the molecular structure for both XB donor and acceptor molecules is presented. The impact of specific structural features is assessed using 19 F and 1 H nuclear magnetic resonance (NMR) titrations to determine association constants, density functional theory calculations for interaction energies and bond lengths, as well as 19 F− 1 H HOESY NMR measurements of intermolecular cross-relaxation between the interacting XB donor−acceptor adducts. For XB donor molecules (perfluoro-halogenated benzenes), results indicate the critical importance of iodine coupled with electron-withdrawing entities. Prominent structural components of XB acceptor molecules include a central atom working in conjunction with a Lewisbase atom to present high electron density directed at the σ-hole (e.g., tributylphosphine oxide). Additionally, larger surrounding aliphatic R groups (e.g., butyl and octyl) were found to significantly stabilize strong XB, particularly in solvents that promote the interaction. With a more thorough understanding of structure-optimized XB, one can envision harnessing XB interactions more strategically for specific design of optimal materials and chemical applications.

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Thiourea‐Based Tritopic Halogen‐Bonding Acceptors

Happonen¹,

Mattila²,

Peshev³

et al. 2023

Chemistry An Asian Journal

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A series of thiourea‐based tritopic receptor molecules were synthesized to be used as building blocks for halogen‐bonded assemblies. Here, 16 new receptor molecules were synthesized from two different 2,4,6‐trialkyl‐1,3,5‐tris(bromomethyl)benzene starting materials via tris(isothiocyanatomethyl)benzene intermediates. The alkyl substituents in the benzene ring proved to be important for isothiocyanate group formation instead of competing thiocyanate group. The synthesis route allowed us to synthesize the isothiocyanate intermediates and further the receptor molecules without the typically used and highly toxic thiophosgene. The synthesized receptor molecules were used to study their halogen‐bond acceptor properties with diiodotetrafluorobenzene donors by single‐crystal X‐ray diffraction method. We were able to obtain five new crystal structures of halogen‐bonded complexes, in which all receptors showed two to four accepted C−I⋅⋅⋅S halogen bonds. The observed halogen bonds were highly directional and showed large variation in C=S⋅⋅⋅I acceptor angles, indicating flexible acceptor properties of sulfur.

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The Se … Hal halogen bonding: Co-crystals of selenoureas with fluorinated organohalides

Cited by 4 publications

References 74 publications

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes

Evaluating Halogen-Bond Strength as a Function of Molecular Structure Using Nuclear Magnetic Resonance Spectroscopy and Computational Analysis

Thiourea‐Based Tritopic Halogen‐Bonding Acceptors

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