Two hybrid materials self-assembly from tetra(isothiocyanate)cobalt(II) dianion and substituted benzyl triphenylphosphinium

Syntheses, crystal structures, weak interaction, magnetic and photoluminescent properties of two new organic–inorganic molecular solids with disubstituted benzyl triphenylphosphinium and tetra(isothiocyanate)cobalt(II) anion

“…The X-ray study reveals that when the F atom in 4-position on the phenyl ring of the cations has been replaced by Cl atom, the crystal system and space group of [2Cl4ClBzTPP] 2 [Co(NCS) 4 ](2) was changed from monoclinic Pc to triclinic P-1. The selected bond lengths and bond angles listed in Table 3 are in fair agreement with those of other molecular solids containing the [Co(NCS) 4 ] 2À anion and substituted benzyl triphenylphosphinium [21][22][23]. Compared to 1, three evident changes in crystal structure are found: (1) the dihedral angles (h 1 , h 2 , h 3 , and h 4 ) change dramatically, and the dihedral angles in 2 are 95.8°, 71.1°, 6.2°and 107.1°for the cation containing P(1) atom, 83.4°, 80.2°, 13.7°and 110.7°for the cation containing P(2) atom, which are significantly different from those of 1; (2) the [2Cl4ClBzTPP] + cations containing P(1) form a 1D column by one pÁ Á Áp interaction [32] between the C(5)-C(10) phenyl rings of the adjacent cations (the vertical distance is 3.600 Å and another pÁ Á Áp interaction between the C(14)@C(15) of C(12)-C(17) phenyl ring and the C(24)-C(29) phenyl rings of the adjacent cations with a centroidÁ Á Ácentroid distance of 3.583 Å (Fig.…”

“…2072 and 2071 cm À1 are the bands of NCS in [Co(NCS) 4 ] 2À anion for 1 and 2, respectively [21]. Bands at 1600, 1586, 1491, 1439 cm À1 for 1 and 1652, 1584, 1473, 1438 cm À1 for 2 can be assigned to m(C@C) of the phenyl rings while the C-Cl stretching vibration band in 1 and 2 is 687 cm À1 , and the m(C-F) band for 1 is 912 cm À1 .…”

“…The transition metal coordination chemistry of thiocyanate or isothiocyanate ligands has extensively been developed for several decades mostly in view of the significance of the corresponding complexes in new fields like crystal engineering, supramolecular chemistry and host-gust chemistry [1,[11][12][13][14][15][16]. The well-known tetrahedral [Co(NCS) 4 ] 2À anion is useful building block, which is in combination with various positively charged moieties and gives rise to molecular solids with diverse physical properties and use as optical, magnetic and conductive materials [17][18][19][20] [21][22][23], in which the effect of the change of the substituted group on the phenyl ring of benzyl group of the cation on the crystal system, space group, weak interactions, the stacking mode of the anions and cations, and the magnetic properties have been systematically investigated. We here present synthesis, FT-IR, UV-Vis spectra, ESI-MS, single crystal structures, weak interactions, magnetic properties and luminescent properties of two new organic-inorganic molecular solids of [Co(NCS) 4 …”

Two Organic Cation Salts Containing Tetra(isothiocyanate)cobaltate(II): Synthesis, Crystal Structures, Spectroscopic, Optical and Magnetic Properties

“…Our previously published studies have been devoted to the syntheses, X-ray single crystal structures, spectroscopic studies, magnetic or fluorescent properties of hybrid materials based on the tetra(isothiocyanate)cobalt/zinc anion and substituted benzyl triphenylphosphonium cations. The examples of [4RBzTPP] 2 [Co(NCS) 4 ] (R = H, F, Br, NO 2 ) [19,20] 4 ] 2, whose crystal structures, spectroscopic, optical and magnetic properties have been investigated. It is of much interest that two solids exhibit dual functionalities such as antiferromagnetic behavior and luminescent activity.…”

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.…”