Luminescence Properties Of Compounds Research Articles

Syntheses, crystal structures, and luminescence properties of three cadmium coordination polymers assembled from a semi-rigid tetracarboxylate ligand

Crystal engineering is considerably useful in the preparation of functional coordination polymers. In the present study, a new semi-rigid tetracarboxylate, 4,5-bis(4-carboxyphenoxy)phthalic acid (H4L), was designed and applied for assembling metal coordination polymers. Self-assembling process involving Cd(II) metal ions, H4L and 4,4′-bipyridine (4,4′-bpy), (E)-1,2-bis(pyridin-4-yl)ethane (bpe) or 1,4-bis(1-imidazolyl)benzene (bib) resulted into the formation of coordination polymers, including [Cd2(L)(4,4′-bpy)1.5(H2O)]n·(H2O)n (1), [Cd2(L)(bpe)1.5(H2O)]n·(H2O)3.5n (2), and [Cd2(L)(bib)1.5]n·(H2O)n (3). Through X-ray single crystal diffraction analysis, the three compounds 1–3 were found to exhibit isostructural three-dimensional polymeric structures composed of two-dimensional secondary layers pillared by different rod-like N-donor ligands. Compared with the uncoordinated H4L exhibiting a symmetric crystal structure, the molecular configurations of L4− in 1–3 were tuned due to the complexation of cadmium ion and the introduction of different N-donors. Additionally, the coordination geometries of cadmium ions and luminescence properties in compounds 1–3 were finely tuned due to the introduction of different lengths of rod-like ligands. The thermostability and luminescence properties of compounds 1–3 were determined. The present results provide further understanding of the crystal engineering of semi-rigid ligands to a certain extent.

Template-directed hierarchical copper(II)-organophosphonate compounds: Syntheses, crystal structures, magnetic and luminescence properties

Three new copper organodiphosphonate compounds, [C4N2H14][Cu(hedph2)2], I, [C4N2H12][Cu3(hedp)2(H2O)4], II and [C6N2H18][Cu3(hedp)2].4H2O, III have been synthesized hydrothermally in the presence of copper nitrate, 1-hydroxyethane-1,1-diphosphonic acid (hedpH4) and various organic aliphatic amines. Molecular structure of compound I is formed in presence of templated 1,4-diaminobutane (DAB). One-dimensional ladder structure of compound II and two-dimensional layer structure of III are observed in the presence of templated piperazine (PIP) and 1,6-diaminohexane (DAH), respectively. The coordination behaviour of the diphosphonate ligand and the organic amines play the crucial role for isolating the different dimensionality amongst the hybrid structures. Although, the compounds II and III display eight-membered rings assembled through vertex-sharing Cu-polyhedra and CPO3 tetrahedra, but the higher coordination mode of diphosphonate ligand can make the 2D layer structure of II instead of 1D ladder of I. The dc-magnetic measurements and theoretical fitting of interacting Cu•••Cu exchange interactions exhibit the antiferromagnetic ordering with weak ferromagnetic coupling in higher-dimensional structures. All the compounds are well characterized by powder XRD, IR, elemental and thermal analysis. The magnetic and luminescence properties of compounds I‒III have also been studied.

Structural Diversity Ranging from Oligonuclear Complexes to 1‐D and 2‐D Coordination Polymers Generated by Tetrasubstituted Adamantane and Spirobifluorene Derivatives

Using tetrahedral and tetragonal spacers, seven new complexes have been obtained: [Co(hfac)2(L1)0.5] 1, [Cu2(hfac)4L2] 2, [Co(hfac)2L2] 3, [Co(hfac)2(L2)0.5]·8H2O 4, [AgL2](SbF6)·CH3COOC2H5 5, [Mn(hfac)2(L3)0.5] 6, [Zn(OAc)2(L3)0.5] 7, {L1 = 1,3,5,7‐tetrakis(4‐cyanophenyl)adamantane, L2 = 2,2′,7,7′‐tetracyano‐9,9′‐spirobifluorene and L3 = 2,2′,7,7′‐tetra(4‐pyridyl)‐9,9′‐spirobifluorene, Hhfac = hexafluoroacetylacetone}. Compound 1 exhibits a 2‐D grid‐like structure with the tetradentate spacer acting as a 4‐connecting ligand. The 2,2′,7,7′‐tetrasubstituted‐spirobifluorene derivatives connect the {MII(hfac)2} entities into a binuclear complex (2), a linear chain (3) and diamond chains (4, 6). The cis or trans configuration of the metal nodes influences the overall topology (MII = CuII, CoII, MnII). Similarly, a 1‐D double chain topological motif results by linking zinc ions and L3 in compound 7. Compound 5 is a 2‐D coordination polymer featuring a layered framework with square cavities. Compound 5 undergoes a reversible single‐crystal‐to‐single‐crystal process, with removal of the solvent molecules (ethyl acetate). The luminescence properties of compounds 5, 7 have been investigated and reveal blue emission with maxima at 402 and 483 nm, respectively. The dynamic magnetic properties and EPR spectrum of 1 have been investigated, revealing the occurrence of slow relaxation of the magnetization that most likely involves a Raman process.

Dicarboxylate‐Induced Structural Diversity of Luminescent Zn(II)/Cd(II) Metal–Organic Frameworks Based on the 2,5‐Bis(4‐pyridyl)thiazolo[5,4‐d]thiazole Ligand

Constructed from rigid 2,5‐bis(4‐pyridyl)thiazolo[5,4‐d]thiazole (Py2TTz) and various dicarboxylic acids [2‐methyl‐1,4‐benzenedicarboxylic acid (2‐CH3‐H2BDC), 5‐methyl‐1,3‐benzenedicarboxylic acid (5‐CH3‐H2BDC), 2,5‐dimethyl‐1,4‐benzenedicarboxylic acid (2,5‐di‐CH3‐H2BDC), 2,5‐dihydroxyl‐1,4‐benzenedicarboxylic acid (2,5‐di‐OH‐H2BDC), 1,4‐naphthalenedicarboxylic acid (1,4‐H2NDC), and 2,6‐naphthalenedicarboxylic acid (2,6‐H2NDC)], nine novel Zn(II)/Cd(II) MOFs have been synthesized under solvothermal conditions. They possess diverse structures, which mainly result from the different shapes and sizes of the auxiliary dicarboxylate ligands. Linear dicarboxylate ligands (2‐CH3‐BDC, 2,5‐di‐CH3‐BDC, 1,4‐NDC, 2,6‐NDC) generate 3D multi‐fold interpenetrated structures, while the V‐shaped dicarboxylate ligand (5‐CH3‐BDC) affords a 2D layer structure. However, linear 2,5‐di‐OH‐BDC results in a 2D layer structure owing to the influence of the hydroxy group. Luminescence properties of compounds 1–9 have been investigated systematically. They display structure‐dependent emission ranging from blue to blue‐white and blue‐green.

Homodinuclear lanthanide 9-anthracenecarboxylate complexes: Field induced SMM and NIR-luminescence

Six homodinuclear lanthanide complexes with formula [Ln2(μ2-9-AC)4(9-AC)2(phen)2] (Ln(III) = Nd (1), Eu (2), Gd (3), Tb (4), Er (5) and Yb (6) are reported and complexes 1–3 and 6 are structurally characterized. 9-HAC = 9-anthracenecarboxylic acid, phen = 1,10-phenanthroline. The luminescence properties of compounds 1–6 have been studied at different temperatures in the solid state and show the sensitization of the 4f–4f emission bands in the NIR range for compounds 1, 5 and 6. The molar magnetic susceptibility measurements of 1–6 in the 2–300 K temperature range indicate weak antiferromagnetic exchange for the isotropic Gd(III) compound 3. Furthermore, slow relaxation of the magnetization is found in complexes 5 and 6 with effective energy barriers of 9.5 cm−1 (0.1 T) and 22.7 cm−1 (0.15 T), respectively.

Syntheses, structures, fluorescence sensing properties and white-light emission of lanthanide coordination polymers assembled from imidazophenanthroline derivative and isophthalate ligands

Nine new lanthanide coordination polymers, namely, [La2(MPIP)2(1,3-bdc)3]n‧5nH2O (1) [Nd2(MPIP)2(1,3-bdc)3]n‧7nH2O (2), [Yb2(MPIP)(1,3-bdc)3]n(3), [Eu2(MPIP)2 (1,3-bdc)2(CH3COO)2]n(4), [Ln2(MPIP)2(1,3-bdc)2(NO3)2]n‧3nH2O (Ln = Tb (5), Gd (6)), [Ln2(MPIP)2(1,3-bdc)3]n‧2nH2O (Ln = Dy (7), Ho (8), Er (9)), MPIP = 2-(3-methylphenyl)imidazo(4,5-f)(1,10)-phenanthroline, H2(1,3-bdc) = benzene-1,3-dicarboxylic acid) have been synthesized under hydrothermal or solvothermal conditions and characterized by IR spectra, elemental analyses, powder X-ray diffraction and single crystal X-ray diffraction. Compounds 1–9 features 1D or 2D lanthanide isophthalate structures bearing large conjugated imidazophenanthroline derivative ligands. The thermal stabilities and luminescence properties of compounds 1–9 were investigated. Based on fluorescence sensing behavior, compounds 4 and 5 display a highly sensitive response toward Fe3+ ion through significant fluorescence quenching. Meanwhile, compound 5 can be used as an indicator to detect acidic and alkali environments. The white light emission was studied by heterogeneous physical mixing components of compounds 1, 4 and 5.

Coordination Polymeric Ensemble of Silver with Nitrate and 4-(Aminomethyl)benzoate: Synthesis, Crystal Structure, and Luminescence Properties

Prismatic crystals of Ag3(4-Amba)2(NO3)2 (I) and Ag(4-AmbaH)NO3 (II) are isolated from the reaction mixture of aqueous solutions of 4-aminomethylbenzoic acid (4-AmbaH) and AgNO3 at Т ≈ 70°C. The crystal structure of compound I (СIF file CCDC no. 1851513) and the luminescence properties of compounds I and II are studied. The structure of compound I contains two crystallographically nonequivalent silver atoms Ag(1) and Ag(2) with the octahedral coordination mode (with allowance for Ag···Ag contacts) with different compositions of the internal spheres of the central atoms. Owing to the contacts, the silver atoms are joined into infinite cluster ribbons (Ag···Ag 3.06−3.27 A). The carboxylate group of the 4-Amba anion exhibits the bridging properties and binds the silver atoms of both types. The Ag(2) atoms also contact with the oxygen atom of the $${\text{NO}}_{{\text{3}}}^{-}$$ ion and coordinate the NH2 group of 4-Amba. The photoluminescence spectra of compounds I and II are of the same type and show the presence of two groups of emission bands with centers at 484 and 543 nm shifted to the red range of the spectrum relative to the band of 4-AmbaH.

Crystal structure, thermal stability and photoluminesence properties of five new Zn(II) coordination polymers constructed from mixed ligand; N-donor pyridine ligands and bis(4-carboxylphenyl)phosphinic acid

Five new Zn(II) coordination polymers, {[Zn2(HBPO)2(phen)2(H2O)2]·H2O}n (1), [Zn2(BPO)(H2BPO)(phen)4]·2(H2BPO)·4H2O (2), {[Zn(HBPO)(4,4′-bipy)0.5]·H2O}n (3), [Zn(HBPO)(dpe)0.5]n (4) and {[Zn2(HBPO)2(dpp)]·H2O}n (5), constructed from mixed ligand; bis(4-carboxylphenyl)phosphinic acid (H3BPO) and N-donor pyridine ligands (phen, 4,4′-bipy, dpe and dpp), have been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy and elemental analyses. Intermolecular hydrogen bonds, π- π interaction and other intermolecular interaction are effective in stabilization of the crystal structure of these supramolecular complexes. The thermal stability and luminescence properties of compounds 1–5 in the solid state were studied too.

Dinuclear LnIII Complexes with 9‐Anthracenecarboxylate Showing Field‐Induced SMM and Visible/NIR Luminescence

The reaction of several Ln(NO3)3·6H2O salts with 9‐anthracenecarboxylic acid (9‐HAC) and 2,2′‐bipyridine (bpy) in a mixture of CH3OH/H2O has allowed the isolation of the dinuclear compounds 1–6 with formula [Ln2(µ2–9‐AC)4(9‐AC)2(bpy)2] [LnIII = Nd (1), Eu (2), Gd (3), Tb (4), Er (5), and Yb (6)]. The molar magnetic susceptibility measurements of 1–6 in the 2–300 K temperature range indicate weak antiferromagnetic exchange for the isotropic GdIII compound 3. Compounds 1, 5, and 6 exhibit field‐induced single‐molecule magnet (SMM) behavior. The luminescence properties of compounds 1–6 in the solid state have been studied at different temperatures and show sensitization of the 4f–4f emission bands in the NIR range for compounds 1, 5, and 6.

A novel double-walled Cd(II) metal–organic framework as highly selective luminescent sensor for Cr2O72− anion

A novel Cd(II) metal–organic framework, [Cd3L3(DMF)2]n (1), was synthesized using 5-(1H-1,2,4-triazol-1-yl)isophthalic acid (H2L) and Cd(NO3)2·6H2O under solvothermal condition. The structure of 1 was characterized by X-ray crystallography, elemental analysis, and IR spectrum. Compound 1 possessed a fascinating three-dimensional (3D) double-walled framework with one-dimensional (1D) channels. The luminescence properties of compound 1 toward anion detection were systematically investigated. The results indicate that compound 1 behaves as a highly selective and sensitive ‘turn-off’ luminescence probe toward Cr2O72− anion.

Magnesium Trimethoxyphenylporphyrin Chain Controls Energy Dissipation in the presence of Cholesterol

A magnesium porphyrin compound, [Mg(TMPP)(H2O)].(CH3COCH3)2H2O 1 (TMPP = 5,10, 15,20-tetrakis(3,4,5-trimethoxyphenyl)porphyrin) has been synthesized and characterized using single crystal X-ray diffraction and other spectroscopic analysis. The luminescence properties of compound 1 were studied at different concentrations. At higher concentration (3 × 10−3 M), treatment of 1 with cholesterol enhanced the luminescence when excited at Soret band, demonstrating the role of lipid in controlling porphyrin-porphyrin interaction for tuning the bulk photophysical properties. However, at lower concentration (10−5 M) of porphyrin, there was no significant change in luminescence intensity in the presence of cholesterol. It suggests some role of lipids in light harvesting systems where chlorophyll is present at higher concentration. A magnesium porphyrin compound, [Mg(TMPP)(H2O)].(CH3COCH3)2H2O 1 (TMPP = 5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl)porphyrin) was synthesized and structurally characterized using single crystal X-ray diffraction and other spectroscopic analysis. The luminescence properties of compound 1 were studied at different concentrations. At higher concentration (3 x 10-3 M), treatment of compound 1 with cholesterol enhanced fluorescence demonstrating the role of lipid in controlling porphyrin-porphyrin interaction for tuning the bulk photo-physical properties.

Luminescence properties of compounds of europium(III) with quinaldic acid and phosphor-containing neutral ligands

Luminescent complex mixed-ligand compounds of europium(III) with quinaldic acid and phosphor- containing neutral ligands have been obtained. Their composition and structure have been determined. The thermal and spectral-luminescent properties of the obtained complex mixed-ligand compounds of europium( III) have been studied. It is shown that, during thermolysis, a water molecule and neutral ligand are detached in two stages with endothermic effects. It is established that quinaldinate ion is coordinated to europium(III) ion in a bidentate fashion. The Stark structure of the 5 D 0–7 F j (j = 0, 1, 2) transitions in low-temperature luminescence spectra of complex compounds of europium(III) has been analyzed.

Structurally Different Calcium(II) Complexes with 5‐Substituted Tetrazole Ligands

AbstractThree different tetrazole‐carboxylate ligands, Hpymtza, Hpytza, and H2dtzeda were chosen to be reacted with Ca(NO3)2·4H2O, resulting in the formation of three coordination compounds, [Ca(pymtza)2(H2O)4] (1), [Ca(pytza)2(H2O)2] (2), and [Ca(dtzeda)(H2O)2] (3) [Hpymtza = 5‐(2‐pyrimidyl)tetrazole‐1‐acetic acid, Hpytza = 5‐(3‐pyridyl)tetrazole‐2‐acetic acid, and H2dtzeda = 1, 2‐bis(tetrazol‐5‐yl)ethane‐N1, N1′‐diacetic acid]. X‐ray diffraction analysis revealed that compound 1 displays a mononuclear structure, compound 2 is a one dimensional zigzag chain structure, whereas 3 shows a three‐dimensional structure. The structures were controlled by not only the different substituents of the tetrazolyl ring, but also the complementary hydrogen bonds. Furthermore, the luminescence properties of compounds 1–3 were investigated at room temperature in the solid state. These emissions can be tentatively attributed to the ligand centered emission.

Structural variation of transition metal coordination polymers based on bent carboxylate and flexible spacer ligand: polymorphism, gas adsorption and SC-SC transmetallation

Reaction of the bent dicarboxylate ligand H2OBA (H2OBA = 4,4′-oxybisbenzoic acid) and the flexible linker 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (L1), under diverse reaction conditions, forms two polymorphic Co(II) coordination polymers (CPs): {[Co(OBA)(L1)]·DMF}n (1), as a three dimensional (3D) framework with a pcu alpha-Po primitive cubic topology, and {[Co(OBA)(L1)]·DMF}n, (2), as a two dimensional (2D) structure with a 6-c uninodal net topology. Gas adsorption measurements of the desolvated Co(II) CPs show negligible uptake of all gases in 1, while 2 exhibits moderate uptake of CO2, with good selectivity over N2 and CH4. With Zn(II), reaction of H2OBA and L1 produces a different 2D CP, {[Zn0.5(OBA)0.5(L1)0.5]}n (3). Finally, three isostructural Cd(II) CPs, {[Cd(OBA)(L1)]·DMF}n (4), {[Cd(OBA)(L1)]·DEF}n (5), and {[Cd(OBA)(L1)]·DMA}n (6) (DMF = N,N-dimethylformamide, DEF = N,N-diethylformamide, DMA = N,N-dimethylacetamide), that differ only in the lattice solvent molecules and show 2D structural arrangements are prepared. Interestingly, CP 4 undergoes single-crystal to single-crystal (SC-SC) transmetallation reaction at room temperature, yielding isostructural {[Cu(OBA)(L1)]·DMF}n (7) that cannot be synthesized independently. Moreover, the luminescence properties of compounds 1, 2, 3, and 4 have been studied in the solid state at room temperature. All the complexes are characterized by elemental analysis, IR, TGA, PXRD and single crystal X-ray diffraction.

Cadmium(ii) carboxyphosphonates based on mixed ligands: syntheses, crystal structures and recognition properties toward amino acids

Three novel cadmium(ii) carboxyphosphonates have been hydrothermally synthesized. The luminescence properties of compounds 1–3 have been investigated. Meanwhile, the excellent abilities of compounds 2 and 3 for selective recognition of tryptophan (Trp) have been demonstrated.

Two fluorescent lead phosphonates for highly selective sensing of nitroaromatics (NACs), Fe3+ and MnO4− ions

Two novel lead(ii) phosphonates have been hydrothermally synthesized. The luminescence properties of compounds 1 and 2 have been investigated. Meanwhile, the selective fluorescent sensing properties of compounds 1 and 2 for p-NP, Fe3+ and MnO4− have also been demonstrated.

Construction of a New ZnII Coordination Polymer for Selective Fluorescence Sensing of CCl4

Solvothermal reactions of Zn(NO3)2·6H2O, H3tci, and biimpy generated a new ZnII coordination polymer namely [Zn3(tci)2(biimpy)]n·2n(DMF) (1 H3tci = tri(2-carboxyethyl)isocyanurate, biimpy = 2,6-bis(1-imdazoly)pyridine, DMF = N,N-dimethylformamide). Single-Crystal X-ray diffraction analysis reveals that compound 1 features a 2-fold interpenetrated 3D pillar-layered framework based on trinuclear [Zn3(COO)6] cluster subunits. Topological analysis reveals that compound 1 represents a 2-fold interpenetrated (3,8)-connected tfz-d topological network with the point symbol of {43}2{46.618.84}. The luminescence properties of compound 1 dispersed in different organic solvents were systematically investigated. The results indicated that compound 1 can be used as a candidate for selective sensing of CCl4 via a luminescence quenching mechanism.

Metal nuclearity affects network connectivity: a series of highly connected metal–organic frameworks based on polynuclear metal clusters as secondary building units

Seven novel highly connected metal–organic frameworks (MOFs), formulated as [Co7(aobtc)3(bpy)2(μ3-OH)2(μ2-OH2)2(H2O)4]·4H2O (1), [Ni5(aobtc)2(bpy)2(μ3-OH)2(H2O)6]·4H2O (2), [Zn3(aobtc)2]·H2bpy·H2O (3), [Zn3(aobtc)2]·H2bpp·H2O (4), [Cd3(aobtc)2]·[Me2NH2]2·3H2O (5), [Co3(aobtc)2]·H2bpp·H2O (6) and [Mn3(aobtc)2]·H2bpy·2H2O (7) (H4aobtc = azoxybenzene-3,3′,5,5′-tetracarboxylic acid, bpy = 4,4′-bipyridine, bpp = 1,3-bis(4-pyridyl)propane) have been synthesized and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analyses. Compound 1 is a 3D (4,4,14)-connected self-penetrating framework with (46)2(45·6)(430·526·631·74) topology based on hexanuclear clusters as 14-connected nodes. To our knowledge, compound 1 represents the highest connected self-penetrating topology presently known in the entangled system. Compound 2 displays a trinodal (4,4,10)-connected network with (46)(45·5)(410·518·612·75) topology based on tetranuclear clusters as 10-connected nodes. Compounds 3–7 exhibit (4,8)-connected flu nets based on trinuclear clusters as 8-connected nodes, and these five MOFs show similar structures but different pore volumes mainly associated with the change of the species of guest molecules. Structural analyses of 1–7 demonstrate that increasing the metal nuclearity is a practical method to obtain highly connected coordination networks based on metal clusters as nodes. In addition, the magnetic properties of 1, 2, 6, and 7 and the luminescence properties of compounds 3–5 have also been studied.

Counterion‐Directed Assembly of Praseodymium(III) Compounds based on the Flexible Ligand 5‐Aminotetrazole‐1‐propionic Acid (Hatzp)

AbstractDifferent kinds of counterions (such as NO3–, ClO4–, and Cl–) play a special role in controlling the framework of coordination compounds. Using this strategy, 5‐aminotetrazole‐1‐propionic acid (Hatzp) was selected to react with praseodymium(III) nitrate or perchlorate in the same solvent system, producing two different coordination compounds, [Pr2(atzp)4(H2O)8]·2NO3·2H2O (1) and [Pr2(atzp)6(H2O)2]·H2O (2). These compounds were structurally characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. X‐ray diffraction analysis revealed that compound 1 displays a dinuclear structure, whereas 2 shows a one dimensional zigzag chain framework. Furthermore, the luminescence properties of compounds 1 and 2 were investigated at room temperature in the solid state.

Construction of New Coordination Polymers from 4’-(2,4-disulfophenyl)- 3,2’:6’3”-terpyridine: Polymorphism, pH-dependent syntheses, structures, and properties

Nine new coordination compounds, namely, [Co(HDSPTP)2(H2O)4]·4H2O (H2DSPTP=4’-(2,4-disulfophenyl)-3,2’:6’3”-terpyridine, 1 and 2), {[Ni(DSPTP)(H2O)4]·3H2O}n (3), {[Cu(HDSPTP)2(H2O)3]·8H2O}n (4), {[Cu(HDSPTP)2(H2O)3]·6H2O}n (5), {[Cu(DSPTP)(H2O)2]·H2O}n (6), {[Zn(DSPTP)(H2O)2]·2H2O}n (7), {[Cd(DSPTP)(H2O)2]·2H2O}n (8), and [Ag2(DSPTP)(H2O)]n (9), were constructed based on a new ligand containing both terpyridyl and sulfo groups. The reactions of H2DSPTP with Co(NO3)2.6H2O resulted in two mononuclear complexes (compounds 1 and 2). They are polymorphisms that display different hydrogen bonding networks. They are selectively synthesized by altering the added alkalis. The reaction of H2DSPTP with Ni(NO3)2·6H2O resulted in a 1D “S-shaped” coordination chain (compound 3). The reactions of Cu(II) with H2DSPTP at different pH value resulted in the following three compounds: two kinds of 1D chains obtained at pH 3.0 and 4.0 for compounds 4 and 5, respectively, and a 3D framework based on binuclear ring units with 4-connected sra topology (Compound 6). The reactions of H2DSPTP with ds-block ions resulted in the following three compounds: a Zn(II) (compound 7) and a Cd(II) (compound 8) 3D frameworks with structures similar to that in compound 6, and a 3D framework based on tetranuclear Ag(I) SBUs with binodal (4,8)-connected flu type 3D framework topology. The structural diversity is mainly attributed to the rich coordination modes (from monodentate to µ7-mode) and conformations (cis–cis and cis–trans) of HDSPTP−/DSPTP2− ligands and the metal center and can be controllable synthesized by altering the alkalis, and pH value. Thermal stability of all compounds was performed, and the thermal behaviors of compounds 6 and 8 were further explored by PXRD. Compound 6 exhibits low thermal stability and undergo a crystalline–crystalline-amorphous phase transition as temperature increases from 25°C to 200°C, and show amorphous–crystalline phase transition when rehydrated. However, compound 8 exhibits high thermal stability above 500°C. Its crystalline phase can retain above 300°C and undergo a crystalline–crystalline phase transition as temperature increased to 400°C, and transit back to compound 8 when rehydrated. Moreover, luminescence properties of compounds 7–9 were also investigated.