Dynamic supramolecular cations in conductive and magnetic [Ni(dmit)2] crystals

Reversible phase transition and thermochromic response in hybrid copper-based perovskites

“…It is a common phenomenon that the dielectric constant could change more significantly near the phase transition temperature. 53,54 To verify whether the titled compound undergoes a phase transition, DSC and dielectric measurements were performed. It can be observed from Fig.…”

Halogen substitution effects on crystal structures and magnetic properties in nickel dithiolate molecular crystals

“…mnt 2À = maleonitriledithiolate dmit 2À = 2-thioxo-1,3-dithiole-4,5-dithiolate) with unique electronic structures and physical properties, have been intensively studied. [18][19][20][21][22][23][24][25][26][27] Too much research effort towards the development of [M(mnt)] À and [M(dmit)] À compounds by rational design of the counter ion structure has been reported. For instance, Nakamura's group [20][21][22] reported the incorporation of a supramolecular M-crown ether cation into the [Ni(dmit) 2 ] À system to yield a molecular metal complex with magnetic and conducting properties and ferroelectricity.…”

Remarkable enhancement of optical and electric properties by temperature-controlled solid-phase molecular motion

“…19,31,32 Fortunately, crown-ether-based supramolecules with the advantages of structural diversity and chemical variability, not only a variety of crown ethers, organic cations and counterions are available, but also some efficient molecular modification strategies can also be employed. 16,17,19,21,33 The first case of crown-ether-based molecular rotator with a polar structure, [( m -FAni)(DB-18-crown-6)][Ni(dmit) 2 ] ( m -FAni = m -fluoroanilinium, DB = dibenzo, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate), which was reported by Akutagawa et al in 2009, was obtained by modifying the organic cation and replacing the crown ether of [(anilinium)(18-crown-6)][Ni(dmit) 2 ] with bulky DB-18-crown-6. 8 In addition, based on H/F substitution of the organic cation of the prototype [(CH 3 –C 6 H 4 –NH 3 )(18-crown-6)][TFSA] (CF 3 –C 6 H 4 –NH 3 = 4-trifluoromethylanilinium), Lv et al discovered a crown-ether-based polar molecular rotator [(CF 3 –C 6 H 4 –NH 3 )(18-crown-6)][TFSA] with a remarkable piezoelectric response.…”

“…[6][7][8][9][10][11][12][13][14] The crown ether molecule can act as a stator to anchor an organic amine by N-H⋯O hydrogen bonds and assembles with the counterion to form a molecular rotator-type system. 12,15,16 This type of molecular rotator is assembled and packed by weaker intermolecular interactions (such as hydrogen bonds, van der Waals bonds and electrostatic force) and therefore, it is conducive to the dynamic motion of the building blocks under external stimuli, which may further lead to significant changes in molecular microstructure and macroscopic physical characteristics. [17][18][19][20] Notably, based on this characteristic, many molecular rotators, such as [Co(NCS) 2 (H 2 O) 2 (4-amino-3-chloropyridine) 2 ](18crown-6), 18 [(MeO-C 6 H 4 -NH 3 )(18-crown-6)](TFSA) (MeO-C 6 H 4 -NH 3 = 4-methoxyanilinium, TFSA = bis(trifluoromethanesulfonyl)ammonium), 19 [(2,2,6,6-tetramethylpiperidine-N-oxyl)(18crown-6)]ReO 4 /ClO 4 , 21 [(2,6-diisopropylanilinium)(18-crown-6)] ClO 4 , 22 (MeO-C 6 H 4 -NH 3 )(18-crown-6)ReO 4 , 23 [(MeO-C 6 H 4 -NH 3 )(18-crown-6)][BF 4 ], 24 have so far been studied and reported for promising applications in intelligent switches, sensors, memorizers, transducers, and so on.…”

“…19,31,32 Fortunately, crown-ether-based supramolecules with the advantages of structural diversity and chemical variability, not only a variety of crown ethers, organic cations and counterions are available, but also some efficient molecular modification strategies can also be employed. 16,17,19,21,33 The first case of crown-ether-based molecular rotator with a polar structure, ] with bulky DB-18crown-6. 8 In addition, based on H/F substitution of the organic cation of the prototype…”