Three molecular metals containing bis(maleonitriledithiolate)nickel(III) anion and 2-substituted benzyl triphenylphosphonium: Syntheses, crystal structures and magnetic properties

Syntheses, one-dimensional chain structures and magnetic properties for two molecular metals of bis(maleonitriledithiolate)nickel(III) anion and disubstituted benzyl triphenylphosphonium

“…S1 Table 5 for the purpose of knowing the effect of the substituent groups and their positions in phenyl ring on the structures of the molecular solids. It can be seen from Table 5 that when the substituted group on ortho-position on benzene ring was fixed, the change of the substituted one on para-position, results in the change of the dihedral angles of cation and the overlapping modes of anions, as well as the Ni· · ·Ni distance, and vice versa [16][17][18][19][20]35]. For example, when the R 2 is F atom, R 1 is changed from H, Cl to Br atom, the crystal system and space group of the molecular solids are changed in the following order: monoclinic (P2 1 /n) → triclinic (P−1) → monoclinic (P2 1 /n), the overlapping modes of anions are changed from Ni· · ·ring and Ni· · ·S → C· · ·ring → Ni· · ·S, and the Ni· · ·Ni distances are changed from 3.939, 4.057, 4.101Å to 7.206Å and 4.148Å.…”

“…Therefore, it is meaningful for the design and preparation of new counter-cations for adjust the overlap patterns of [Ni(mnt) 2 ] − anions in order to build a relationship between the intermolecular and its function. In recent years, we have systemically investigated the influence of derivatives of 2 or 4-substituted benzyl triphenylphosphonium ([2RBzTPP] + and [4RBzTPP] + , R = H, F, Cl, Br, NO 2 ) as multifunctional counter-cation of upon the overlapping mode of the neighboring [Ni(mnt) 2 ] − anion and the magnetic coupling of the molecular metals, which generally involve aromatic · · · stacking, weak coordinative forces, short-range interactions and hydrogen bonds [16][17][18][19][20]. With a view to extending our study in this field, we have obtained two molecular solids containing disubstituted benzyl triphenylphosphonium cations, [2F4BrBzTPP] [Ni(mnt) 2 [21,22].…”

Syntheses, crystal structures and properties of two new molecular solids by self-assembly of bis(maleonitriledithiolate)nickel(III)/copper(II) anion and substituted 4-fluorobenzyl isoquinolinium cation

“…Since the first molecular metal containing [Ni(mnt) 2 ] À (mnt = maleonitriledithiolate) with ferromagnetic ordering at the low temperature, NH 4 Á[Ni(mnt) 2 ]ÁH 2 O, was reported in 1996, much concern has been increasingly given to [M(mnt) 2 ] À (M = Ni, Pd, Co or Pt) anions in the field of materials, so there was a very important expand in concept [9][10][11][12][13]. In the past years, our lab and other scholars have already successful synthesized and reported a series of new molecular materials by utilizing substituted benzylpyridinium ([RBzPy] + ) and substituted benzyltriphenylphosphonium ([RBzTPP] + ) as counter cations of the [Ni(mnt) 2 ] À anion, and the [Ni(mnt) 2 ] À anion could form an ideal 1D zigzag magnetic chain through intermolecular NiÁ Á ÁS, SÁ Á ÁS, NiÁ Á ÁNi or pÁ Á Áp interactions, and these materials exhibit diverse magnetic properties [14][15][16][17]. In addition, our main objective is to find more suitable organic counter cations to tune the stacking mode of [M(mnt) 2 ] À anions and obtain some hybrid inorganicorganic materials with novel magnetic properties [18,19] 2À = maleonitriledithiolate) were prepared and characterized, and the influence of the substituted groups and the different anions on the crystal stacking structures and magnetic properties of the solids is investigated when the cations is 1-(4 0 -fluorobenzyl) isoquinolinium ([4FBzIQl] + ) and the metal ion is changed from Ni (III) to Cu(II) ion.…”