Syntheses, structures, and properties of nine d¹⁰or p-block coordination polymers based on a ligand containing both terpyridyl and sulfo groups

Abstract

Nine new coordination compounds, namely, {[Zn(HDSPTP) 2 (H 2 O) 4 ]·6H 2 O} n (H 2 DSPTP = 4'-(2,4disulfophenyl)-4,2':6'4''-terpyridine, 1), [Cd(DSPTP)(H 2 O) 2 ] n (2), {[Ag(HDSPTP)]·30H 2 O } n (3), 10 {[Ag(HDSPTP)(H 2 O)]·3H 2 O} n (4), [Ag 2 (DSPTP)] n (5), {[Ag 4 (DSPTP) 2 (H 2 O) 3 ]·2H 2 O} n (6), [Pb(DSPTP)(H 2 O) 2 ] n (7), {[Pb(DSPTP)(H 2 O) 3 ]·3H 2 O} n (8), and [PbK(DSPTP)(NO 3 )(H 2 O) 2 ]·H 2 O} n (9), were synthesized by introducing a ligand with both terpyridyl and sulfo groups as organic linkers. The reaction of H 2 DSPTP with Zn(II) salts only resulted in a mononuclear complex (compound 1), in which most donor groups appear uncoordinated, whereas in the reaction with Cd(II) salts under similar conditions 15 resulted in a three-dimensional (3D) twofold interpenetrated dia framework (compound 2). The reactions of H 2 DSPTP with AgCF 3 CO 2 or AgNO 3 resulted in compounds 3-6 with different structures: a porous supramolecular framework via interlaced packing of one-dimensional (1D) coordination chains (compound 3), a two-dimensional (6,3) network based on coordination bonds and Ag···O interactions (compound 4), a 3D framework based on 1D [Ag 2 (2-SO 3 − ) 2 ] n secondary building block (compound 5), and a twofold 20interpenetrated framework with a binodal (4,6)-connected fsh topology based on planar tetranuclear SBUs as nodes (compound 6). The reactions of H 2 DSPTP with Pb(NO 3 ) 2 resulted in the following three compounds: a 3D twofold interpenetrated dia framework (complex 7), a twofold interpenetrated (6,3) network (compound 8), and a 3D complicated framework based on tetranuclear SBUs, double-bridge DSPTP 2− ligands, and [K(H 2 O)] + species (compound 9). The structural diversity is mainly attributed to the rich coordination 25 behaviors of HDSPTP − /DSPTP 2− ligands and the metal center and can be controllable synthesized by altering the metal to ligand ratio, alkalis, and pH value for Ag(I) and Pb(II) compounds. Compound 2 exhibits high thermal stability above 500 °C, undergo a crystalline-amorphous-crystalline phase transmission as temperature increased from 25 °C to 500 °C, and show amorphous-crystalline phase transition when rehydrated. Moreover, luminescence properties of all the compounds were also investigated. 30 65 structures compared with those based on 4'-(2,4-Disulfophenyl)-2,2':6'2''-Terpyridine ligand, which we reported previously. 10

Isomers of Terpyridine as Ligands in Coordination Polymers and Networks Containing Zinc(II) and Cadmium(II)

“…For the divergent 4,2′:6′,4″-tpy, [Cd( 52 )(OH 2 ) 2 ] n (H 2 52 is defined in Figure 35 ) is a sole example of a cadmium(II)-containing coordination polymer with a sulfonato-functionalized 4,2′:6′,4″-tpy ligand for which structural data are available. Two independent reports of the synthesis and structure of [Cd( 52 )(OH 2 ) 2 ] n appeared in 2015 [ 95 , 96 ]. The compound was prepared under hydrothermal conditions from H 2 52 and either CdCO 3 or CdCl 2 ·2.5H 2 O, and crystallizes in the triclinic space group P –1.…”

“…The large voids in a single net result in 2-fold interpenetration ( Figure 35 b). Interestingly, when zinc(II) acetate combined with H 2 52 under the same hydrothermal conditions as for the preparation of [Cd( 52 )(OH 2 ) 2 ] n , single crystals of the mononuclear complex [Zn(H 52 ) 2 (OH 2 ) 4 ]·6H 2 O were obtained and PXRD data confirmed that the single crystal was representative of the bulk material [ 95 ]. The preference for mononuclear over polymeric assembly is not readily explained.…”

A Cu(II) MOF with laccase-like activity for colorimetric detection of 2,4-dichlorophenol and p-nitrophenol

“…According to the research of Zhao et al , 44 copper ions can promote the single electron transfer of electron-rich organic molecules and effectively mediate the oxidative-coupling reaction. Considering the coordinated group, the sulfonic acid group is a weaker electron donor compared with the carboxyl group and water molecule, 45 and the copper coordinated with the oxygen of the sulfonic acid group tends to require electrons from outside. In other words, in the catalytic reaction of oxidizing phenols, copper prefers to obtain electrons from phenols, which facilitates the catalytic reaction and thus leads to higher catalytic activity.…”

Constructing chiral MOFs by functionalizing 4,2′:6′,4′′-terpyridine with long-chain alkoxy domains: rare examples of neb nets

“…In addition to the widespread use of pyridinyl [5][6][7] and carboxylate [8][9][10][11][12][13] functionalities, sulfonate donors have also been used to access 3D frameworks. 14 3D-networks utilizing only the two pendant donors of the 4,2′:6′,4″-tpy domain are relatively rare, although the reaction of 4′-(pyridin-2-yl)-4,2′:6′,4″-tpy and CoIJNCS) 2 gives a 3D structure in which the pyridinyl substituent is not coordinated. 15 This is an unusual case where combination of a simple 4,2′:6′,4″-tpy ligand and Co(NCS) 2 leads to a 3D framework; more usually, 2D (4,4) or (6,3) nets result.…”