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Unusual Behavior of Donor-Acceptor Stenhouse Adducts in Confined Space of a Water-Soluble Pd-8(II) Molecular Vessel

Saha, Rupak and Devaraj, Anthonisamy and Bhattacharyya, Soumalya and Das, Soumik and Zangrando, Ennio and Mukherjee, Partha Sarathi (2019) Unusual Behavior of Donor-Acceptor Stenhouse Adducts in Confined Space of a Water-Soluble Pd-8(II) Molecular Vessel. In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 141 (21). pp. 8638-8645.

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Official URL: http://doi.org/10.1021/jacs.9b03924

Abstract

Donor-acceptor Stenhouse adducts (DASA) are new-generation photochromic compounds discovered recently. DASA exist normally in open form (blue/violet) and readily convert to cyclic (light yellow/colorless) zwitterionic form reversibly in the presence of green light in toluene/dioxane. In aqueous medium, the open form is not stable and converts to the cyclic zwitterionic form irreversibly. We report here a new self assembled Pd8 molecular vessel (MV) that can stabilize and store the open form of DASA even in aqueous medium. Reaction of the 90 acceptor cis-(tmeda)Pd(NO3)(2) (M) tmeda = N,N,N',N'tetramethylethane-1,2-diamine] with a symmetric tetraimidazole donor (L, 3,3',5,5'-tetra(1H-imidazol-1-y1)-1,1'-biphenyl) in a 2:1 molar ratio yielded a water-soluble 8+4] self-assembled M8L4 molecular barrel (MV). This barrel (MV) is found to be a potential molecular vessel to store and stabilize the open forms of DASA in aqueous medium over the more stable zwitterionic cyclic form, while in the absence of the barrel the same DASA exist in cyclic zwitterionic form in aqueous medium. The hydrophobic interaction between the cavity and the open form of DASA molecules benefits reaching an out-of-equilibrium or reverse equilibrium state in aqueous medium. The presence of excess MV could even drive the conversion of the stable cyclic form to the open form in aqueous medium. The host guest complex is stable upon irradiating with green light. To the best of our knowledge, this is the first successful attempt to stabilize the open form of DASA molecules in aqueous medium and the first report on the fate of DASA in a confined space discrete molecular architecture. Furthermore, the molecular vessel has been utilized for catalytic Michael addition reactions of a series of nitrostyrene derivatives with 1,3-indandione in aqueous medium.

Item Type: Journal Article
Additional Information: copyright for this article belongs to JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 24 Jun 2019 20:16
Last Modified: 24 Jun 2019 20:16
URI: http://eprints.iisc.ac.in/id/eprint/63049

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