A series of thermal stable lanthanide porphyrins with a condensed three-dimensional porous open framework: Gas adsorption and magnetic properties

Abstract

A series of lanthanide porphyrins, [Ln III (TPPS IV )] n • nH 5 O 2 (Ln = La, Sm, Eu; H 2 TPPS = tetra(4-sulfonatophenyl)porphyrin), have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction. These compounds are characterized by a condensed three-dimensional (3-D) porous open framework. Magnetic measurements reveal that these compounds show ferromagnetic, antiferromagnetic and paramagnetic behavior, respectively. All of the compounds exhibit highly thermal stability. The FT-IR and adsorption measurement of CO 2 were also studied.

Preparation, Crystal Structures, and Properties of a Series of Crystalline Tetra(4-sulfonatophenyl)porphyrinato Histidine 4f-3d Porphyrinic Compounds

“…When the temperature is lowered from 300 to 2 K, the μ eff slowly decreases to a value of 2.16 μ B at 2 K. The data of χ M vs T were analyzed using the well-known Curie–Weiss model to yield C = 0.59 K and a negative Weiss constant θ = −0.06 K, indicating the existence of antiferromagnetic behavior in complex 1 . Magnetic behaviors of lanthanide porphyrins with antiferromagnetic interactions have been reported previously . The curves of χ M vs T and μ eff vs T for complex 2 are presented in Figure b, of which the χ M means the magnetic susceptibility for per Eu 2 Co 2 unit (Eu 3+ ion: S = 1 with ground state 7 F 1 and low-spin Co 2+ ions: S = 1/2).…”

“…The diagrams of χ M vs T and μ eff vs T of complex 1 are given in Figure 5a, of which the χ M is the Magnetic behaviors of lanthanide porphyrins with antiferromagnetic interactions have been reported previously. 40 The curves of χ M vs T and μ eff vs T for complex 2 are presented in Figure 5b, of which the χ M means the magnetic susceptibility for per Eu 2 Co 2 unit (Eu 3+ ion: S = 1 with ground state 7 F 1 and low-spin Co 2+ ions: S = 1/2). The μ eff at 300 K is 2.34 μ B , which is smaller than the expected value of 2.45 μ B for noninteracting free ions per Eu 2 Co 2 unit.…”

Porphyrin and phthalocyanine-based metal organic frameworks beyond metal-carboxylates

“…MOFs structures diversity remains quite limited; mostly lanthanide-based materials have been reported. A series of isotopic Ln-based MOFs were reported by Chen et al [53][54][55][55][56][57][58][59][60][61][62][63][64] these 3-D structures are based on rod-like inorganic secondary building units (SBU) where the Ln ions are bridged by eight sulfonates from eight different porphyrins. All the sulfonates display the same  2 , 2 bidentate binuclear coordination mode: they are coordinated by two O atoms in a bridging mode and leave the third pending oxygen free (Figure 1a).…”

“…When a metal is inserted inside the porphyrin, it is usually connected to the metal centre of the neighbouring macrocycle by either a bridging water molecule (divalent Zn and Co) or by an oxo ligand in case of V(IV) (Figure 1c). In case of a free base or divalent metalloporphyrin, the framework is anionic and the charge is balanced by an hydronium, giving the overall formula: [LnM(TSPP)H3O]n 57,[59][60][61][62] or : [LnH2(TSPP)H3O]n [54][55][56]58,63,64 . For one of the reported compounds, a crystal structure of the N2 containing framework was solved, although in bulk measurements none of the sample proved to be intrinsically porous to N2.…”

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

“…202 Later, another series of hybrid assemblies were synthesized, which were composed of meso-tetrapyridylporphyrin and various lanthanide complexes. 203 solvothermal methods used various solvents, water [205][206][207][208] or organic solvents, 203,204,209,210 as well as different reaction times and temperatures. Unfortunately, most lanthanide-based MOFs did not take advantage of the special spectroscopic properties of lanthanides, and the choice of lanthanides was not really targeted for a given property, but because most of these ions have similar size and coordination numbers.…”