Syntheses, weak interactions, 3D network structures and magnetic properties of two salts based on bis(maleonitriledithiolate)copper(II) anion and substituted triphenylphosphonium cation

Abstract

Two new salts, [BzTPP] 2 [Cu(mnt) 2 ] (1) and [4NO 2 BzTPP] 2 [Cu(mnt) 2 ](2) (BzTPP ? = benzyltriphenylphosphonium and mnt 2-= maleonitriledithiolate) have been prepared and characterized by elemental analyses, UV, IR, molar conductivity and single-crystal X-ray diffraction. The single-crystal structure analysis shows that 1 crystallizes in the monoclinic space group P2 1 /n, while 2 crystallizes in the triclinic space group P-1. The effects of weak intramolecular interactions such as C-HÁÁÁO, C-HÁÁÁS, C-HÁÁÁN, C-HÁÁÁCu hydrogen bonds and pÁÁÁp, pÁÁÁp stacking interactions in the solids generate a 3D network structure. It is noted that the change in the molecular topology of the counteraction when the 4-substituted group in the benzyl ring is changed from H to NO 2 results in differences in the crystal system, space group, weak interactions and the stacking mode of the cations and anions of 1 and 2. The magnetic susceptibilities of these salts measured in the temperature range 2.0 to 300 K show weak ferromagnetic coupling features with h = 2.05 9 10 -2 K for 1 and 5.13 9 10 -3 K for 2.

Syntheses, Weak Interactions, and 3D Network Structures of Two Hybrid Salts Containing Bis(iso-maleonitriledithiolate)nickelate(II) Anion and Substituted Chlorobenzyl Triphenylphosphinium Cation

“…This weak hydrogen bonding with Ni(II) is rare and unusual but not unprecedented, [20,30] which is similar to the C-H···Cu observed in the literature. [13,31] These complicated weak interactions between the anions and the cations further generate a 3D network structure for 1 (Figure 2c). …”

“…[1][2][3][4][5] For example, a subsequent study of the corresponding salts showed multifunctional organic cations such as substituted pyridinium or triphenylphosphinium derivatives as the counterions can effectively mediate the stacking pattern of anions or cations and the magnetic coupling between the spin carriers [M(mnt) 2 ] n− (M = Ni, Pd, Pt, Cu; n = 1 or 2, mnt 2− = maleonitriledithiolate). [6][7][8][9][10][11][12][13] Isomaleonitriledithiolate (i-mnt) is a geometrical isomer of mnt, the corresponding compounds have been rarely investigated, [14][15][16] but the crystallography results show that imnt ligand can form mono-, di-, and multinuclear complexes with many transition metals and some main group ions. [17][18][19] Recently, we have synthesized and characterized several salts containing [Ni(i-mnt) 2 ] 2− anion and some courtercations.…”

Syntheses, crystal structures, luminescent properties of two new molecular solids with tetra(isothiocyanate)zinc(II) and substituted benzyl triphenylphosphonium cations

“…In the meanwhile, many zinc(II) compounds have aroused a great deal of interest due to their intriguing structural diversities and potential applications on luminescent materials, and the ligands which containing hetero-aromatic rings can effectively enhance the fluorescence emissions of compounds and are currently of interest in the development of fluorescent materials [17][18][19]. In recent years, our research group has used [RBzTPP] + (R = X, NO 2 or CN; TPP = triphenylphosphonium) to adjust the stacking mode of the some inorganic complex anions such as [Ni(mnt) 2 ] − and [Cu(mnt) 2 ] 2− (mnt 2− = maleonitriledithiolate), [Ni(i-mnt) 2 ] 2− (i-mnt 2− = iso-maleonitriledithiolate), [Ni(tdas) 2 ] 2− (tdas 2− = 1, 2, 5-thiadiazole-3,4-dithiolate) and [Co(NCS) 4 ] 2− (NCS − = isothiocyanate), and obtained several molecular materials [20][21][22][23][24][25][26][27][28][29]. As part of our continuing studies, substituted benzyl triphenylphosphonium cations are firstly introduced into the system containing [Zn(NCS) 4 The white single crystals suitable for the X-ray structure analysis were obtained by slowly evaporating the solution of 1 and 2 in MeOH about two weeks at room temperature.…”

Syntheses, Characterization, and Crystal Structures of Two Tetrachlorocobaltate(II) Salts With 4-Substituted Benzyl Triphenylphosphonium

“…[3,5] Our interest is in the preparation of a series of multifunctional organic cations, derivatives of [RBzTPP] + (R = X, NO 2 , or CN; TPP = triphenylphosphine), to tune the stacking mode of the complex anions such as [Ni(mnt) 2 ] -and [Cu(mnt) 2 ] 2-(mnt 2-= maleonitriledithiolate), [Ni(i-mnt) 2 ] 2-(i-mntt 2-= iso-maleonitriledithiolate), and [Ni(tdas) 2 ] 2-(tdas 2-= 1, 2, 5-thiadiazole-3,4-dithiolate)], have obtained several molecular materials. [13][14][15][16][17][18][19] …”