Solid state double [2 + 2] photochemical reactions in the co-crystal forms of 1,5-bis(4-pyridyl)-1,4-pentadiene-3-one: establishing mechanism using single crystal X-ray, UV and 1H NMR

Santra, Ramkinkar; Biradha, Kumar

doi:10.1039/c0ce00612b

Cited by 54 publications

(23 citation statements)

References 80 publications

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“… 17 − 19 In the case of pyridine derivatives in the crystal, this can be accomplished by supramolecular templating by metal complexes, 20 resorcinol (pyridine-containing monoenones 21 and acyclic dienones 22 ) or by treatment with silver ions (only pyridine-containing acyclic dienones were studied). 23 …”

Section: Introductionmentioning

confidence: 99%

Structure–Property Relationships of Dibenzylidenecyclohexanones

et al. 2022

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A series of symmetrical dibenzylidene derivatives of cyclohexanone were synthesized with the goal of studying the physicochemical properties of cross-conjugated dienones (ketocyanine dyes). The structures of the products were established and studied by X-ray diffraction, NMR spectroscopy, and electronic spectroscopy. All products had the E , E -geometry. The oxidation and reduction potentials of the dienones were determined by cyclic voltammetry. The potentials were shown to depend on the nature, position, and number of substituents in the benzene rings. A linear correlation was found between the difference of the electrochemical oxidation and reduction potentials and the energy of the long-wavelength absorption maximum. This correlation can be employed to analyze the properties of other compounds of this type. The frontier orbital energies and the vertical absorption and emission transitions were calculated using quantum chemistry. The results are in good agreement with experimental redox potentials and spectroscopic data.

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Section: Introductionmentioning

confidence: 99%

Structure–Property Relationships of Dibenzylidenecyclohexanones

et al. 2022

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“…Biradha and Santra also showed that 1,5-bis(4-pyridyl)-1,4pentadiene-3-one does not crystallise in the required geometry for both CLC double bonds to react, but a single [2+2] cycloaddition was found to occur. 17 A 5-methoxyresorcinol and phloroglucinol co-crystal leads to a successful [2+2] cycloaddition involving both CLC double bonds. Hydrogen-bonding to the pyridyl ring systems align the CLC double bonds favourably for [2+2] cycloaddition.…”

Section: Introductionmentioning

confidence: 99%

Photochemical-mediated solid-state [2+2]-cycloaddition reactions of an unsymmetrical dibenzylidene acetone (monothiophos-dba)

et al. 2012

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A novel unsymmetrical dibenzylidene acetone (monothiophos-dba, compound 3), containing two chemically different alkene moieties, undergoes a selective photochemically-induced [2+2] cycloaddition solid-state transformation (single crystal and powder), as shown by X-ray diffraction methods. In the single crystal the rate constant for the cycloaddition reaction was determined {k = (2.3 ¡ 0.1) 6 10 24 s 21 }, with a 69% conversion attained, which compares well with a twophoton irradiation experiment using a Nd:YAG laser pumped dye laser at 605 nm radiation (66% conversion). Full conversion was attained using powdered 3 after 43 h. A similar conversion was noted between the single crystal and powder forms (59% and 66% conversion after 5 h irradiation). Irradiation of monothiophos-dba in solution using a 325 nm laser, and monitoring by 1 H NMR spectroscopy, showed that no cycloaddition occurred, but exclusive photochemically-induced trans A cis isomerisation of the alkene bond connecting the unsubstituted aryl group (cis A trans isomerisation in these electron-deficient and polarised CLC bonds occurs rapidly by thermal equilibration).

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“…With the aim of gaining deeper insight into the PHL hydrogen-bonding capability, a search of the CSD (Groom et al, 2016) has been performed of all its co-crystals of known structure. Excluding disordered structures, 30 entries have been found (Santra & Biradha, 2011;Boldog et al, 2004;Haberhauer et al, 2004;Ung et al, 1994;Biradha & Zaworotko, 1998;Gao et al, 2008;Arora et al, 2009;Bis et al, 2007;Santra & Biradha, 2008;Sarma et al, 2008;Mahapatra et al, 2010;Lavender et al, 1998;Shi et al, 2010;Ghosh et al, 2005;Coupar et al, 1996;Barooah et al, 2003;Vishweshwar et al, 2003;Imai et al, 2009;Hou et al, 2010;Liu et al, 2001), two of which are simple solvated PHL [solvent: dimethylsulfoxide (Polyanskaya et al, 2011) and water (Thomas et al, 2011)]. The complete list of CSD entries, together with information on the co-crystals' composition and donorÁ Á Áacceptor distances of O-H(hydroxyl)Á Á ÁX interactions, considering only those in which the PHL hydroxyl group acts as a donor, are reported in Table S6 of the supporting information.…”

Section: Hydrogen-bonding Analysismentioning

confidence: 99%

Supramolecular hydrogen-bonding patterns of co-crystals containing the active pharmaceutical ingredient (API) phloroglucinol andN-heterocycles

Cvetkovski

Bertolasi

Ferretti

2016

Acta Crystallogr Sect B

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The active pharmaceutical ingredient phloroglucinol (PHL) has been taken as an illustrative molecule to explore the intermolecular interactions which can be established with other molecular entities to build PHL pharmaceutical co-crystals. The crystal structures of five newly synthesized co-crystals are reported, where PHL is crystallized with N-heterocycles, namely 2-hydroxy-6-methylpyridine (1), 2,4-dimethyl-6-hydroxypyrimidine (2), 4-phenylpyridine (3), 2-hydroxypyridine (4) and 2,3,5,6-tetramethylpyrazine (5). The structural characteristics of these co-crystals, as far as the hydrogen-bonding networks and the crystalline architectures are concerned, are strongly dependent on the chemical features of the coformer molecules, as well as on their size and shape. A detailed analysis of the intermolecular interactions established in all the PHL co-crystals of known structures has allowed the recognition of some regularities in the packing modes that can be useful in the design of new supramolecular adducts forming predictable structural motifs.

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Solid state double [2 + 2] photochemical reactions in the co-crystal forms of 1,5-bis(4-pyridyl)-1,4-pentadiene-3-one: establishing mechanism using single crystal X-ray, UV and 1H NMR

Cited by 54 publications

References 80 publications

Structure–Property Relationships of Dibenzylidenecyclohexanones

Structure–Property Relationships of Dibenzylidenecyclohexanones

Photochemical-mediated solid-state [2+2]-cycloaddition reactions of an unsymmetrical dibenzylidene acetone (monothiophos-dba)

Supramolecular hydrogen-bonding patterns of co-crystals containing the active pharmaceutical ingredient (API) phloroglucinol andN-heterocycles

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