para-Benzene disulfonic acid and its tetrachloro and tetrafluoro derivatives—studies towards polyhalogenated metal–organic-frameworks with sulfo analogues of terephthalic acid

Abstract

We developed convenient synthetic routes for the preparation of para-benzene disulfonic acid (H(2)BDS) and its tetrachloro (H(2)BDSCl(4)) and tetrafluoro (H(2)BDSF(4)) derivatives. The reaction of these acids with zinc nitrate in DMF led to single crystals of [Zn(BDS)(DMF)(2)] (triclinic, P ̄1[combining macron], Z=2, a=976.62(4), b=986.85(4), c=1014.40(4), α=69.106(2)°, β=68.746(2)°, γ=86.295(2)°, wR(2)=0.0627), [Zn(BDSCl(4))(DMF)(4)] (triclinic, P ̄1[combining macron], Z=1, a=831.5(1), b=905.2(1), c=989.6(1), α=90.44(2)°, β=91.41 (2)°, γ=106.72(2)°, wR(2)=0.0635), and [Zn(BDSF(4))(DMF)(4)] (monoclinic, P2(1)/c, Z=2, a=889.01(3), b=968.91(3), c=1633.07(5) pm, β=106.524(2)°, wR(2)=0.0948). While [Zn(BDS)(DMF)(2)] exhibits a layer structure, the disulfonate linkers connect the zinc ions into chains in the crystal structures of [Zn(BDSCl(4))(DMF)(4)] and [Zn(BDSF(4))(DMF)(4)]. Thermoanalytical investigations revealed that desolvation of the compounds occurs in a temperature range between 100 and 200 °C. The solvent free sulfonates show remarkably high stabilities, [Zn(BDS)(DMF)(2)] is stable up to nearly 600 °C. The halogenated acids were also used to prepare copper salts from aqueous solutions and Cu(2)(OH)(2)(CO(3)) (malachite) as a copper source. The crystal structure of [Cu(H(2)O)(6)](BDSF(4)) (triclinic, P ̄1[combining macron], Z=1, a=510.45(2), b=744.68(3), c=1077.77(4) pm, α=85.627 (2)°, β=77.449 (2)°, γ=76.015 (2)°) exhibits complex cations and uncoordinated sulfonate anions, while in [Cu(BDSCl(4))(H(2)O)(4)] (orthorhombic, Pnma, Z=4, a=721.27(2), b=2147.81(6), c=979.42(3) pm) the Cu(2+) ions are linked to infinite chains in the crystal structure. The most interesting structural feature of [Cu(BDSCl(4))(H(2)O)(4)] is the significant deviation from planarity of the disulfonate dianion. Theoretical investigations revealed that a boat conformation is favoured due to steric hindrance in cases where a syn coordination of the sulfonate groups occurs. The thermal behaviour of the copper compounds was also investigated by DTA/TG measurements and X-ray powder diffraction.

Syntheses and Reactions of 2,5‐Disulfobenzene‐1‐diazonium Salts: Towards Functionalized Sulfonate Metal–Organic Frameworks

“…For this reason, we previously developed a route to disulfonic acid 1 from 1,4-dibromobenzene (6). Production of 1 from 6 required oxidation of critical intermediate 1,4-benzenedithiol (7; Scheme 2).…”

“…We recently reported on the zinc salt of benzenedisulfonic acid, which showed even higher stability (decomposition above 600°C) than the corresponding copper(II) counterpart. [6] We now report the development of a flexible approach to benzenedisulfonic acids 4 bearing an additional substituent X, which may enable the preparation of MOFs with functionalized pores. To introduce substituent X by post-synthetic transformations of a MOF, [7] we employed diazonium salt 4 with X = N 2 + as a common precursor to all other derivatives.…”

Crystal structure of di-acetato-bis-pyridine-palladium(II), [Pd(C2H3O2)2(C5H5N)2], C14H16N2O4Pd

“…For several years we explored the potential of sulfonic acids for the construction of frameworks (MOFs) and coordination polymers [4][5][6][7][8][9][10]. In the course of introducing catalytically active metal atoms such as palladium in the desired coordination complexes the usage of Pd(OAc) 2 as the starting material resulted in the here presented compound, which has been prepared and characterized up to now only via IR and elemental analysis but without structure elucidation [11].…”

1,4-Benzenedisulfonic acid (H2BDS) as terephthalic acid analogue for the preparation of coordination polymers: the examples of M(BDS)(NMP)3(M = Mn, Fe, Co; NMP = N-methylpyrrolidone)

“…Syntheses Manganese(II) (1,4-benzenedisulfonate)tris(N-methylpyrrolidone) Mn(BDS)(NMP) 3 . A mixture of 25 mg of Mn(CH 3 COO) 3 Á2H 2 O (0.093 mmol), 20 mg of H 2 BDSÁ2H 2 O (0.073 mmol), and 3 ml of NMP was filled into a glass ampoule.…”