Polynuclear Cd^II Polymers: Crystal Structures, Topologies, and the Photodegradation for Organic Dye Contaminants

Abstract

To systematically explore the effect of polynuclear complexes on photocatalytic degradation of the organic dyes, a series of coordination complexes containing CdII clusters, formulated as {[Cd3L2(H2O)5]·H2O} n (1), {[Cd3L2(hbmb)(H2O)2]·2.5H2O} n (2), {[Cd3L2(btbb)(H2O)2]·2EtOH·1.5H2O} n (3), and {[Cd6L4(bipy)2(H2O)6]·3H2O} n (4) (H3L = 3,4-bi(4-carboxyphenyl)-benzoic acid, hbmb = 1,1′-(1,6-hexane)bis(2-methylbenzimidazole), btbb = 1,4-bis(2-(4-thiazolyl)benzimidazole-1-ylmethyl)benzene, 4,4′-bipy = 4,4′-bipyridine), have been designed and synthesized. Complex 1 based on trinuclear CdII clusters exhibits a new (3,3,6)-connected 3D framework. 2 belongs to a (3,3,8,8)-connected tfz-d topology net with pillar-layered frameworks assembled by two kinds of trinuclear CdII clusters. 3 is a 3D pillar-layered framework, which features a (3,8)-connected tfz-d net based upon one kind of trinuclear CdII cluster. 4 presents a new 3D (3,6,10)-connected framework with dinuclear and tetranuclear clusters. The photocatalytic properties of complexes 1–4 have been studied in detail. Remarkably, 1–4 all reveal good photocatalytic activity in MB/MO degradation. The optical energy gap calculated by the diffuse reflectivity spectra of 1–4 are consistent with their degradation rates. Moreover, the experimental results further demonstrate that the cluster complexes containing different kinds of nuclei may exert different impact on the decomposition of disparate organic dyes.

Photocatalytic Decontamination of Wastewater Containing Organic Dyes by Metal–Organic Frameworks and their Derivatives

“…[36b]; tpcb = tetrakis(4-pyridyl)cyclobutane; [44] pz = pyrazine; [45] L = 3,4-bi(4-carboxyphenyl)-benzoic acid, bipy = 4,4'-bipyridine; [46] btec = 1,2,4,5-benzenetetracarboxylate, bptc = 3,3',4,4'-benzophenone tetracarboxylic acid; [47,60] [58];L = 3-pyridylnicotinamide, ADTZ = 2,5-(s-acetic acid)dimercapto-1,3,4-thiadiazole; [48,49] en = ethylenediamine, AT = 5,5-azotetrazolate; [50] PTZ = 2-pyridyltetrazolato; [51] tptc = terphenyl-3,3',5,5'-tetracarboxylic acid, bidb = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene; [53] 4-bpt = 3,5-bis-(4-pyridyl)-1,2,4-triazole; [25] tipm = tetrakis[4-(1-imidazolyl)phenyl]methane; [55] bpp = 1,3-bis(4-pyridyl)propane; [56,93,100] bdoa = benzene-1,4-dioxyacetica cid, ttbt = 10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene; [57] bpy = 2,2'-bipyridine,p ytz = 4-(1 H-tetrazol-5-yl)pyridine; [37b, 59] phen = 1,10-phenanthroline; [60,72] cpb = 1,3-(3',4'-carboxylphenoxy)benzene; [61] Ta bH = 4-(trimethylammonio)benzenethiol, bpe = 1,2-bis(4-pyridyl)-ethylene; [62] L = bis-(3,5-dicarboxyphenyl)terephthalamide; [63,73,80] L 2 = N,N'-bis(3-pyridinecarboxamide)-1,3-propane; [65] L = N,N'-bis(pyridine-3-yl)-5-methylisophthalic dicarboxamide, tpd = 2,5-thiophenedicarboxylic acid, mip = 5-methylisophthalic acid, hip = 5-hydroxyisophthalica cid; [66] atrz = 4-amino-1,2,4-triazole; [67] pzca = 2-pyrazine carboxylic acid; [68] TATAB* = 4,4'-[ 6-(dimethylamino)-1,3,5-triazine-2,4-diyl]bis(azanediyl)dibenzoica cid; [69] bmib = 1,3-bis(2-methylimidazol-1-ylmethyl)benzene;…”

Construction of Four Zn(II) Coordination Polymers Used as Catalysts for the Photodegradation of Organic Dyes in Water

“…Such as, using the known CPs {[Zn 2 (Tipa)(4,4 1 -bpdc) 1 5 ]¨H 2 O} n (H 3 bcb = 3,4-bi(4-carboxyphenyl)-benzoic acid) [26] as catalysts, ca. 82.0%, 92.7% and 88.7% of MB was degraded in 120, 140 and 180 min, respectively.…”

“…In addition, the PXRD patterns of each powder for 1-4 were basically identical to those of the parent compounds, indicating that these compounds are stable during photocatalysis. [26] as catalysts, ca. 82.0%, 92.7% and 88.7% of MB was degraded in 120, 140 and 180 min, respectively.…”

“…Recently, considering the novelty of this field in CPs, much effort has been devoted to developing new photocatalytic materials based on CPs in the degradation of many kinds of organic contaminants with up to 90% efficiency [24][25][26][27][28]. Compared to the traditional semiconductor metal oxide, the advantages of CPs as photocatalyst lie in the fact that their combination of inorganic and organic moieties results in different metal-ligand charge transfer, which can give rise to tunable photocatalysts [29].…”

Syntheses and Characterization of Three Coordination Polymers of Zinc(II) and Cadmium(II) with Dicarboxylates and Bis(thiabendazole) Ligands

“…Introducing one thiazole group at the ortho-position of the coordinating N atom may optimize the photophysical property and biological activity [9,10]. Furthermore, the selection of the flexible bis(thiabendazole) ligands with different spacers is based on the following considerations: (i) the bis(thiabendazole) ligands provide more potential coordination sites, which could meet the coordination requirements of metal centers; (ii) these ligands can be regarded as bridges to build high dimensional frameworks; (iii) these ligands have diverse flexibility and conformational freedom by -(CH 2 ) n -backbones, offering different capacities for spatial extension [11][12][13]. So far as we know, there has little if anything been mentioned about CPs based on flexible bis(thiabendazole) ligands according to the Cambridge Structural Database (version 5.37, Feb 2016 plus 1 update) [14].…”