Unusual structural effects of intermolecular π-bonding in the tetracyanopyrazine (ion-radical) dimer

Rosokha, Sergiy V.; Lu, Joan; Han, Bing; Kochi, Jay K.

doi:10.1039/b812829d

Cited by 27 publications

(30 citation statements)

References 43 publications

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“…The existence of multivariant orientations in ion radical associates has already been demonstrated in studies based on experimental X‐ray diffraction data. Twisted complexes have, for instance, already been reported with thianthrene, tetracyanopyrazine, and naphthalene derivatives83–85 but to our knowledge, such arrangements have neither been observed nor considered with viologen π‐dimers for which the sole structure reported so far corresponds to a fully “eclipsed” conformation 86. Our results thus point out the clear importance of the substituents introduced on the terminal nitrogen atoms of the pyridinyl radicals.…”

Section: Resultsmentioning

confidence: 52%

Chemically and Electrochemically Triggered Assembly of Viologen Radicals: Towards Multiaddressable Molecular Switches

Kahlfuss

Métay

Duclos

et al. 2014

Chemistry A European J

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We have established that bipyridinium radicals can be reversibly π-dimerized under the combined effects of chemical (proton transfer) and electrochemical (electron transfer) stimuli. Our investigations also led to the discovery that a bis-pyridinyl appended calixarene intermediate is involved in a fully reversible redox-triggered σ-dimerization process. The structure of the most stable intramolecular σ-dimer was provided by computational chemistry and its complete conversion into a noncovalent π-dimer could be triggered chemically by addition of protons, leading to the formation of protonated cation radicals. Theoretical data collected with the N-methylated and N-protonated π-dimers also support the existence of multivariant orientations in π-bonded dimers of viologen cation-radicals.

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Section: Resultsmentioning

confidence: 52%

Chemically and Electrochemically Triggered Assembly of Viologen Radicals: Towards Multiaddressable Molecular Switches

Kahlfuss

Métay

Duclos

et al. 2014

Chemistry A European J

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“…For this family of acceptors, any spontaneous electron transfer from the donor to the acceptor is accompanied by a lengthening of the cyanide bond distances as electrons are donated into the group's antibonding p*-orbitals [44,45]. Upon comparing the cyanide bond distances for TCNP in its neutral form to those in 2, the mean cyanide bond distance in the former is 1.141(2) Å , while in the latter it was found to be 1.143(2) Å [46]. In addition to the analysis of the terminal nitrile bond distances in 2, all remaining bonds including those within the pyrazine ring and those responsible for binding the nitrile group to the ring of TCNP were compared to the literature values reported for its neutral form, and further suggested that the acceptor within 2 exists as a neutral molecule.…”

Section: X-ray Crystallographymentioning

confidence: 89%

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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“…[17] To understand the state of the radicala nionso f SQC À in the o-dichlorobenzene solution,w ecarried out EPR experiments under reduction of this dye by potassium graphite Chem. Generally, radicala nionsh ave as trong tendency to dimerize and form diamagnetic singlyb ondedd imers.…”

Section: Synthesismentioning

confidence: 99%

“…The charge state of indium atoms remains unchanged even on reduction of In III (Pc 2À )t o In III (PcC 3À ). As ingle CÀCb ond formed betweent wo squarylium radicala nionsh as the length of 1.563 (5) ,w hich is typical for dimers of such type [17] andc lose to the length of the C(sp 3 )ÀC(sp 3 )b ond (1.54 ). All four bonds in this ring have similar lengths.…”

Section: Crystal Structuresmentioning

confidence: 99%

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl‐Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers

Konarev

Kuzmin

Khasanov

et al. 2018

Chemistry A European J

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Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K )}{(cis-indigo-O,O) Ti (Pc )}(Cl )⋅C H Cl (1), {cryptand(K )}{(cis-thioindigo-O,O) In (Pc )} ⋅C H Cl (2), and {cryptand(K )}{[(SQ) -O,O] In (Pc )} ⋅3.5 C H Cl (3) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans-indigo or trans-thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to Ti Pc or In Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ ) dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to In Pc. Dianionic Pc macrocycles have been found in 1-3. The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines.

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Unusual structural effects of intermolecular π-bonding in the tetracyanopyrazine (ion-radical) dimer

Cited by 27 publications

References 43 publications

Chemically and Electrochemically Triggered Assembly of Viologen Radicals: Towards Multiaddressable Molecular Switches

Chemically and Electrochemically Triggered Assembly of Viologen Radicals: Towards Multiaddressable Molecular Switches

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

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl‐Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers

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