Layered, Two-Dimensional Hydrogen Bonding Nets in the Structure of the 1:1 Encounter Complex TMTTF–TCNB: Combined Structural and Spectroscopic Study

Reinheimer, Eric W.; Rivas, M.; Zhao, Huaiqing; Dunbar, Kim R.

doi:10.1007/s10870-011-0021-y

Cited by 10 publications

(2 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The organocyanide acceptor tetracyanobenzene (TCNB) is known to form charge transfer complexes with multiple organic donors. Among these are complexes with condensed aromatic compounds, , aromatic and conjugated amines, − and sulfur-containing heterocyclic compounds (tetrathiafulvalene and its derivatives). − Despite the fact that a large number of complexes of organic and heterocyclic compounds with TCNB are already known, no π-complexes of azaphospholes with TCNB [or other π-acceptors of this class (TCNE and TCNQ)] have been described in the literature. This can be partially explained by the lack of donor properties of azaphospholes.…”

Section: Introductionmentioning

confidence: 99%

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

et al. 2020

View full text Add to dashboard Cite

Herein, we present the synthesis, single-crystal X-ray structures, and spectroscopic properties for the 1:1 donor−acceptor complexes of 1,2,4,5-tetracyanobenzene (TCNB) with annelated 3a,6a-diaza-1,4-diphosphapentalenes (DDPs) based on cyclohexanone azine (2) and tetralone azine (4). These are the first complexes of an organic π-acceptor with donor phosphorus heterocycles. According to the X-ray study, the DDPs and TCNB molecules are alternately stacked with interplanar distances of 3.335 and 3.404 Å for 2 and 4, respectively, which are suitable for intermolecular π•••π interactions. The bond lengths and angles in the component molecules agree with values for neutral species, and the infrared spectra indicate a very slight degree of ionicity. The estimated HOMO−LUMO gap from the onset of optical absorption (1.40 eV) is in agreement with the band gap estimated from the density functional theory calculations for 2 (1.47 eV). By contrast, in a reaction with the related electron acceptor, tetrachloroterephthalonitrile, the DDPs proved to be donors of lone electron pairs in a nucleophilic aromatic substitution reaction of chlorine atoms demonstrating the duality of their electronic nature.

show abstract

Section: Introductionmentioning

confidence: 99%

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

et al. 2020

View full text Add to dashboard Cite

show abstract

“…The frequency shift for compound 7 (15 cm À 1 ) turned out to be the maximum, and it is larger than the corresponding shifts for TCNB complexes with compounds 1 and 2 (9 and 7 cm À 1 , respectively). For comparison, also note that infrared spectra obtained for TCNB complexes with bis(methylenedithio)tetrathiafulvalene [29] and 2,3,6,7-tetramethyl-1,4,5,8tetrathiafulvalene (1 : 1) [30] show cyanide stretching frequencies of 2240 cm À 1 and 2244 cm À 1 respectively suggesting that no perceptible charge transfer has occurred between the TTF donor and acceptor. The principal CÀ H stretching bands (3047 and 3113 cm À 1 ) in free tetracyanobenzene were downshifted (Figure S7) upon formation of the adduct (7, 3098 and 3030 cm À 1 , respectively; 8, 3085 and 3025 cm À 1 , respectively), which is attributed to the formation of close intermolecular contacts [C(sp 2 )À H•••NÀ C(sp 2 )] between TCNB molecules lying parallel on the crystallographic c axis.…”

Section: Ir Spectroscopymentioning

confidence: 99%

3 a,6 a‐Diaza‐1,4‐Diphosphapentalenes: Synthesis and Complexation with the Organic π‐Acceptor 1,2,4,5‐Tetracyanobenzene

et al. 2023

View full text Add to dashboard Cite

The reaction of PCl 3 with diethyl ketazine and 4-phenylcyclohexanone azine results in the formation of 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes which were reduced by magnesium in THF to give corresponding diazadiphosphapentalenes EtMeDDP and PhcHexDDP, containing two-coordinate phosphorus atoms. According to the CVA data, the new diazadiphosphapentalenes are strong electron donors showing oxidation peak potentials at 0.34 and 0.10 V, respectively, (vs. Ag/AgCl). Interaction of 1,2,4,5-tetracyanobenzene (TCNB) with the obtained diazadiphosphapentalenes in any stoichiometry produces sandwich complexes of the composition DDP-TCNB-DDP. Black-purple crystals of π-complexes contain infinite molecular chains with short P•••P contacts between DDP molecules and short (Csp 2 À H•••N) contacts between TCNB molecules. Calculations showed that each TCNB molecule is an acceptor of ~0.3e from two DDP molecules. Estimation of the HOMO-LUMO gap from the onset of optical absorption give values of 1.25 eV and 1.31 eV for [(EtMeDDP) 2 (TCNB)] and [(PhcHexDDP) 2 (TCNB)] respectively.

show abstract

Highlighting Intermolecular Contacts and Spectral Properties in a New Organic Donor–Acceptor Complex: Synthesis, Structure and Infrared Spectroscopy of MT-TCNB (MT = bis(methylenedithio)tetrathiafulvalene)

Fisher

Reinheimer

2013

J Chem Crystallogr

View full text Add to dashboard Cite

Layered, Two-Dimensional Hydrogen Bonding Nets in the Structure of the 1:1 Encounter Complex TMTTF–TCNB: Combined Structural and Spectroscopic Study

Cited by 10 publications

References 77 publications

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

3 a,6 a‐Diaza‐1,4‐Diphosphapentalenes: Synthesis and Complexation with the Organic π‐Acceptor 1,2,4,5‐Tetracyanobenzene

Highlighting Intermolecular Contacts and Spectral Properties in a New Organic Donor–Acceptor Complex: Synthesis, Structure and Infrared Spectroscopy of MT-TCNB (MT = bis(methylenedithio)tetrathiafulvalene)

Contact Info

Product

Resources

About