Inclusion of a dithiadiazolyl radical in a seemingly non-porous solid

Abstract

Inclusion of the dithiadiazolyl radical PhCNSSN˙ into the dynamically porous metallocycle [Cu(L1)Cl], where L1 is the bidentate ligand 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, has been achieved by gas phase diffusion. Single crystal X-ray diffraction, powder X-ray diffraction, UV-visible spectroscopy, EPR and SQUID magnetometry studies confirm inclusion of the radical into this seemingly non-porous material, and illustrate the antiferromagnetic coupling between the paramagnetic host and guest species. The radical guest is readily released by heating or by the addition of solvent (CHCl).

A merged copper(I/II) cluster isolated from Glaser coupling

“…Besides, magnetic susceptibility measurements on 2 by SQUID magnetometry result in an increase of χ m T values along with the rising of the temperature (Supplementary Fig. 10), confirming an antiferromagnetic coupling system in complex 2 44 . As complex 2 is EPR silent, DOSY experiment was then performed to demonstrate that the structure retains intact in solution.…”

Investigation of Various Organic Radicals Dispersed in Polymethylmethacrylate Matrices Using the Electron Spin Resonance Spectroscopy Technique

“…Small and structurally simple molecules that can be used as probes are also studied using this technique. − The electron spin resonance (ESR) spectroscopy is a powerful technique that can be used for the detection of organic radicals confined in the nanospaces of the material and nitroxide (NO) groups bonded to the material. The temperature dependence of the molecular dynamics of the confined radicals or NO moieties in the nanospace is studied to gain information on the structures, sizes, and shapes of the nanospaces present in porous materials, − crystals, polymers, liquid crystals, supercooled bulk water, biological membranes, , and proteins − using the ESR spin probe technique. The dynamics of the moieties bearing the unpaired electrons are influenced by the structures or shapes of the nanospaces.…”

“…The values of the g tensor and the hyperfine interaction ( A ) tensor of the unpaired electron are determined by analyzing the dynamics of the moieties bearing the unpaired electrons. The ESR spin probe techniques can be divided into two categories: (i) the spin-label method executed by functionalizing the NO groups in the material ,,,, and (ii) the method where the free radicals such as 4-substituted 2,2,6,6-tetramethyl-1-piperidinyloxyl (4- R -TEMPO; 1 : TEMPO ( R = H) and 2 : 4-hydroxy-TEMPO (TEMPOL; R = OH); Figure a) are physically adsorbed in the confined spaces. ,,− ,,,, …”

“…The ESR spin probe techniques can be divided into two categories: (i) the spin-label method executed by functionalizing the NO groups in the material 9,14,19,21,23 and (ii) the method where the free radicals such as 4-substituted 2,2,6,6-tetramethyl-1-piperidinyloxyl (4-R-TEMPO; 1: TEMPO (R = H) and 2: 4-hydroxy-TEMPO (TEMPOL; R = OH); Figure 1a) are physically adsorbed in the confined spaces. 7,8,[10][11][12][13]16,17,20,22 In the past decade, the ESR spin probe technique has been used to study the organic 1D nanochannels of 2,4,6-tris (4chlorophenoxy)-1,3,5-triazine and (o-phenylenedioxy)cyclotriphophazene crystals using 2-substituted nitronylnitroxide (2-X-NN, 3−5, Figure 1b). 24,25 Nitronylnitroxide (NN) radicals are common organic radicals.…”

Dithiadiazolyl radicals as building blocks for molecular materials

“…A DTDA has been included in a porous metallocyclic host in an effort to produce materials with interesting magnetic behaviour through interaction between the radical and the host (Fig. 1 right) [4]. The coordination of DTDAs to metalloporphyrins has also been extensively investigated.…”