Identification and Analysis of a 2:1 Monoclinic Phase for the Organic Donor–Acceptor Complex o-Me2TTF-TCNB: Structural and Spectroscopic Studies of a New Solid State Configuration

Fisher, Steven P.; Reinheimer, Eric W.

doi:10.1007/s10870-014-0497-3

Cited by 5 publications

(4 citation statements)

References 56 publications

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“…These groups, present on TCNB as well as other organocyanide acceptors such as TCNQ and TCNE, shift to lower frequency values upon reduction of the acceptor. 29,38 The infrared spectra for complexes 2 and 4 and for TCNB showed cyanide stretching frequencies of 2236, 2238, and 2245 cm −1 , respectively (Figures S3 and S4). Undoubtedly, a shift to lower frequencies with a difference of 9 cm −1 (for 2) or 7 cm −1 (for 4) does not provide a clear definition of charge transfer, especially if we take into account the fact that the structural data indicate the presence of neutral components.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…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%

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

et al. 2020

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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.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…For a qualitative assessment of charge transfer in DA complexes containing terminal CN groups it is convenient to use IR spectroscopy. Such groups present in organocyanide acceptors (TCNB, TCNE, TCNQ) show a shift to lower frequency values upon reduction of the acceptor [27,28] . Infrared spectra obtained for TCNB and complexes 7 , 8 showed cyanide stretching frequencies of 2245, 2230, and 2238 cm −1 , respectively (Figure S7).…”

Section: Ir Spectroscopymentioning

confidence: 98%

“…Such groups present in organocyanide acceptors (TCNB, TCNE, TCNQ) show a shift to lower frequency values upon reduction of the acceptor. [27,28] Infrared spectra obtained for TCNB and complexes 7, 8 showed cyanide stretching frequencies of 2245, 2230, and 2238 cm À 1 , respectively (Figure S7). 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).…”

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

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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.

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Utilizing Perylene in New Organic Donor–Acceptor Materials: Highlighting the Synthesis, Structure and Physical Properties of Perylene-pDNB and Perylene-TCNP

et al. 2015

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In this communication, we present the syntheses, structure, infrared (IR) spectroscopic, and electronic transport properties for two new Perylene-containing donor-acceptor complexes, Perylene-pDNB (1) and Perylene-TCNP (2). The 2:1 complex with pDNB, complex 1, crystallizes in the triclinic space group P " 1 with cell dimensions a = 7.7488(12) Å , b = 9.7125(15) Å , c = 10.6864(17) Å , a = 80.829(7)°, b = 84.893 (7)°and c = 89.495(6)°, while complex 2, the 1:1 complex with TCNP, crystallizes in the orthorhombic space group Cmca with a = 18.264(4) Å , b = 7.405(2) Å and c = 14.674(3) Å . Structural features of the constituent donor and acceptor molecules were compared to those for the free components and, when coupled with IR spectroscopic measurements, suggested that both complexes contained neutral components. This conclusion was further supported by electronic transport measurements that revealed both complexes to be insulators. Graphical Abstract Herein we present the structure and both the IR spectroscopic and transport properties for new

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Identification and Analysis of a 2:1 Monoclinic Phase for the Organic Donor–Acceptor Complex o-Me2TTF-TCNB: Structural and Spectroscopic Studies of a New Solid State Configuration

Cited by 5 publications

References 56 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

Utilizing Perylene in New Organic Donor–Acceptor Materials: Highlighting the Synthesis, Structure and Physical Properties of Perylene-pDNB and Perylene-TCNP

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