Kacper Paszczyk, Krystyna A. Deresz, Radosław Kamiński, Patryk Borowski, Dominik Schaniel, Adam Krówczyński and Katarzyna N. Jarzembska*,
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引用次数: 0
Abstract
Two analogous photoswitchable square-planar nitrite coordination compounds of NiII and PdII with the (N,N,O)-donor (1-phenyl-3-(2'-picolylimino)prop-2-en-1-one) ancillary ligand, Ni-1a and Pd-1a, are reported. The samples were thoroughly characterized (photo)crystallographically, spectroscopically, and computationally. Ni-1a crystallizes in the P1̅ space group with one molecule comprising the asymmetric unit, whereas Pd-1a tends to form polymorphic (Pd-1a and Pd-1a′) and solvatomorphic (with dichloromethane: Pd-1a-DCM and with chloroform: Pd-1a-CHCl3) crystal structures. In the Ni-1a crystal structure, the nitro binding mode is dominant; however, some traces of the endo-nitrito isomer are detected, whereas for the palladium derivative, purely the nitro form is observed for all the crystal forms in the 100–290 K temperature range. Ni-1a, Pd-1a, and Pd-1a-DCM are efficient photoswitches working between 100 and 200 K, with conversions as high as 80–100% upon 470–530 nm light-emitting diode irradiation. At 200 K and above, the decrease in population of the photogenerated product is observed. Under continuous light irradiation, some notable population of the endo-nitrito isomer can be generated and crystallograhically detected also at higher temperatures (up to around 240 K). In the case of Ni-1a, the endo-nitrito form is generated faster, and its decay is slower at 200 K and at higher temperatures than for Pd-1a. It should also be noted that for Pd-1a, only one symmetry-independent molecule is photoswitchable. In turn, the Pd-1a′ and Pd-1a-CHCl3 systems appeared nonphotoactive. Such behavior can be explained by the energetic factors, nitrite group orientation, and the shape of the reaction cavity. Interestingly, a strong linear correlation between the M···M distance in the crystal structures of the examined photoswitches and the population of the endo-nitrito form is noted.
期刊介绍:
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.