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Self-Assembled Pd(II) Barrels as Containers for Transient Merocyanine Form and Reverse Thermochromism of Spiropyran

Howlader, Prodip and Mondal, Bijnaneswar and Purba, Prioti Choudhury and Zangrando, Ennio and Mukherjee, Partha Sarathi (2018) Self-Assembled Pd(II) Barrels as Containers for Transient Merocyanine Form and Reverse Thermochromism of Spiropyran. In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 140 (25). pp. 7952-7960.

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Official URL: https://dx.doi.org/10.1021/jacs.8b03946


Self-assembly of a cis-blocked Pd(II) 90 degrees ditopic acceptor cis-(tmeda)Pd(NO3)(2)] (M) with a tetradentate donor L-1 benzene-1,4-di(4-terpyridine)] in 2:1 molar ratio yielded two isometric molecular barrels MB1 and MB3 in DMSO tmeda = N,N,N'N'-tetramethylethane-1,2-diamine]. Exclusive formation of the symmetrical tetrafacial barrel (MB1) was achieved when the self-assembly was performed in aqueous medium. The presence of a large confined cavity makes MB1 a potential molecular container. Spiropyran (SP) compounds exist in stable closed Spiro form in visible light and convert to transient open merocyanine (MC) form upon irradiation with UV-light or upon strong heating. The transient MC form readily converts to the stable closed SP form in visible light. MB1 has been employed as a safe container to store the planar and unstable merocyanine isomers (MC1/2) of different spiropyran molecules (SP1/2) SP1/2 = 6-bromo-spiropyran and 6-nitrospiropyran] for several days. The transient MC forms (MC1 and MC2) were found to be stable inside the molecular container MB1 under visible light and even in the presence of different stimuli such as heat and UV light for a long time. Such stabilization of MC forms inside the confined cavity of MB1 is noteworthy. This phenomenon was generalized by utilizing a carbazole-based molecular barrel (MB2) as a host, which also showed a similar stabilization of transient MC form in visible light at room temperature. Moreover, reverse thermochromism was observed as a result of heating of the MC1 subset of MB2 complex, which de-encapsulates the guest in the form of SP1 to give a colorless solution. Moreover, both the host molecules (MB1, MB2) were capable of stabilizing transient MC2 even in the solid state. Such stabilization of transient MC forms in the solid state and transformation of SP forms to MC forms in the solid state in the presence of molecular barrel are remarkable, and these properties have been employed in developing a magic ink.

Item Type: Journal Article
Additional Information: Copyright of this article belong to AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 25 Jul 2018 15:28
Last Modified: 25 Jul 2018 15:28
URI: http://eprints.iisc.ac.in/id/eprint/60293

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