ARTICLE ‘eyanides, their most distinguishing property appears to be a switchable dielectric behaviour, demonstrated for several ‘compounds comprising alkylammonium?*-*, formamidinium!, {guanidinium?2, acetamidinium®*, imidazolium™=*3 and (CHs},NOH" (TMAO") cations? [At this juncture, a broader comment has to be made on an analogue compound, [(CHs),NOH],[KFe(CN},] (TMAO-Fe).” For this compound, 9 multi-axial room temperature (RT) ferroelectricity was demonstrated, with the spontaneous polarization of 0.58 Cem? high T, of 402 K and 24 equivalent ferroelectric directions. Without a doubt, multi-axial ferroelectricity on its own merit isa highly desirable property, asit allows one to orient the polarization of the sample with the ‘electric field along more than one axis. Nevertheless, the Uniqueness of this material lies in the underlying bond- switching mechanism of the phase transition. Crystallographic studies revealed that upon going from paraelectric to ferroelectric phase, K-N bonds are replaced with K-O ones, where © atoms come from the hydroxyl groups of TMAO* cations. Indeed, bond switching phenomenon is uncommon for hybrid perovskites, for which the primary mechanism of ferroclectricto-paraelectric phase transition disorder type, Le. the organic cations located in the cavities ‘order at low temperatures; this Is typically assisted by some degree of distortion of the metalorganic cage, but the connectivity between metal cations and organic linkers remains Untouched. Although TMAO-Fe can be classified as high-temperature Ferroelectric (as for organic-inorganic hybrid), the stability range of the HT phase of TMAO-Fe is relatively narrow. This property of TMAO-Fe is an obvious drawback for practical applications, as the low separation between T. and the decomposition temperature leaves litle margin for an error, ‘making this material potentially susceptible to thermal damage Upon relatively small temperature jumps. This raises the ‘question of whether thermal properties of this material can be altered in a beneficial way by targeted component substitution, ‘a strategy widely and successfully) employed in hybrid perovskites. Clearly, a replacement of the A-site organic cation is not an option here, as TMAG' ions are directly responsible for bond-switching phenomenon, but the substitution of B-site ‘metal ion (Fe™) to the other trivalent cation of similar chemistry appeared to us the right way to go. in effect, in this contribution, ‘we present [(CHs]sNOH|a{KCo(CN)e] (TMAO-Co}, a Co¥-based analogue of TMAO-Fe. As desired, TMAO-Co revealed improved thermal stability. Indeed, for TMAO-Co the Curie temperature (7) is shifted to a higher value of ca. 416 K (improvernent by ca, 10K versus TMAO-Fe), as well as the separation between T, and the decomposition threshold, is of 46 K. Of particular relevance here is that TMAO-Co preserves good ferroelectric property of its archetype, as revealed by the dielectric hysteresis loop measurements along a and c crystallographic directions, with spontaneous polarizations values of 0.9 and 0.63 Cem? at 293 K.A deeper understanding of the bi-axial ferroelectric property is of order- 2) J. Name., 2012, 00, 1-3 Journal Name has been garnered from DFT theoretical studies that allowed for the resolution of structural determinants which contribute to the direction-dependent polarization values, Moreover, the changes in domain structure that take place during ferroelectri-to-paraelectric phase transition been captured using temperature-resolved optical microscopy. Upon studies on TMAO-Co, it also emerged that relative Intensity of SHG response of ferroelectric phase of TMAO-Co is a. two times higher than that TMAO-Fe, and is coupled with much enhanced optical stability to femtosecond irradiation. This allowed us to demonstrate robust high: temperature SHG switching between SHG-on and SHG-off states for TMAO-Co. Finally, a complementary set of temperature-resolved Raman and IR spectroscopic methods has been employed to gain a complete spectroscopic view on order-disorder Phenomena, distortion of polyhedral units and changes in the hydrogen-bonding network, These measurements also strongly point to the thermal stability and phase transition reversibility in TMAO-Co. have 2. Experimental details 2.1, Preparation All reagents (analytical grade) used for the synthesis were commercially purchased from Sigma-Aldrich and used without further purification. Trimethylamine N-oxide hydrochloride (TMAC- was synthesized by the reaction of the trimethylamine N-oxide lhyérate ( 299%, Sigma-Aldrich, 10g, 0.09mol) with 36.5% aqueous Hcl (9g, 0.09mol) in 50 ml of ethanol. Next day, white crystals were "insed by methanol and dried by flowing nitrogen. The stoichiometry cof the obtained compounds was confirmed by an elemental analysis to be for TMAO-CI: C: 32.10% (theor. 32.30%), N: 12.3% (theor. 12,554), H: 9.01% (theor. 9.03%). The compounds TMAO-Co, and TMAO-e were obtained as block pale-yelow and dark orange crystals, respectively, by evaporation at room temperature of stoichiometric amounts of K;Co/Fe(CN), (0.013 mol) and trimethylamine N-oxide hydrochloride (0.027 mol) in aqueous solution (50m!) (Fig). TMAO-Co or TMAO-Fe crystals were harvested after one week with the 71% yield of the products . The stoichiometry of the obtained compounds was confirmed by an elemental analysis to be for TMAO-Co C: 35.23% (theor. 35.57%), W: 26.9% {theor. 27.57%), H: 4.93% (theor, 4.96%) and for TMAO:Fe C: 35.82% (theor, 35.74%, N: 27.3% (theor, 27.79%), H: 4.91% (theor. 5.00%). A powder X-ray citfracion verified the phase purity (see Fg S1, ESI) Powder X-ray diffraction was recorded using X’Pert PRO powder diffractometer operating with Cu Ka radiation. 2.2.Thermal analysis Differential scanning calorimetry (OSC) runs were recorded with calorimeter witha scanning rate of 10 Kmin* on coaling/esting in the temperature range of 290-460 K. The TGA/OSC measurements ‘were performed on Metler Toledo TGA/DSC 3+ instrument between ‘This journal is © The Royal Society of Chemistry 20x