Diphthalic Acid Research Articles

SOLVOTHERMAL SYNTHESIS, STRUCTURE, AND PROPERTIES OF CADMIUM(II)-ORGANIC COORDINATION POLYMER CONTAINING CARBOXYL GROUPS

Under the conditions of solvothermal synthesis, a new metal-organic coordination polymer of the composition Cd[H2L] (I, H4L = 4,4'-([2,2'-bipyridine]-6,6'-diylbis(oxy))diphthalic acid). According to X-ray diffraction analysis, each Cd(II) cation binds four organic ligands: one via the coordination of the chelate bipyridyl fragment, two via the bidentate coordination of deprotonated COO groups, and one more via the monodentate coordination of the protonated carboxylate group. The obtained three-dimensional metal-organic framework does not contain free space capable of including guest molecules. Compound I was characterized by powder X-ray diffraction, IR spectroscopy, elemental (C, H, N) and thermogravimetric analyses, and luminescence spectra were recorded for it.

A comparative study of proton conduction between two new Cd(II) and Co(II) complexes and in vitro antibacterial study of the Cd(II) complex

Two new complexes based on 4,4′‐[1,3‐phenylenebis(oxy)]diphthalic acid (H4L) ligands were synthesized, namely, [Cd2(L)(1,10‐phen)2(H2O)]n(1) and [Co2(L)(1,10‐phen)2(H2O)]n(2), in which 2D structures transform into 3D supramolecular structures by CH···π interaction. The proton conductivity of complexes 1 and 2 at low temperature is close (σ1 = 3.12 × 10−8 S cm−1 and σ2 = 3.81 × 10−8 S cm−1 at 30°C), but these two complexes show different conduction mechanisms. The Vehicular mechanism in 1 is caused by the O···H/H···O contact in 1, which is stronger than 2, and the Grotthuss mechanism in 2 is caused by the N···H/H···N contact in 2, which is stronger than 1. At the same time, complex 1 showed excellent antibacterial properties in vitro, mainly reflected in that five kinds of bacteria (Escherichia coli, Bacillus amyloliquefaciens, Pantoea agglomerans, Pseudomonas putida, and Pectobacterium carotovora) could play an obvious inhibitory effect in the concentration range of 20 μg·ml−1.

Construction of turn-on mode fluorescent sensor for Pb<sup>2+</sup> and Al<sup>3+</sup> with structure of phthalic acid and tetraphenylethylene core

<p indent="0mm">Lead is one of the most hazardous metals to humans. It accumulates in liver, kidney and central nervous system, and interferes with a variety of physiological processes such as biosynthesis of hemoglobin. Lead is especially dangerous for children, causing mental retardation. Aluminum has an important role in Alzheimer’s disease, Parkinson’s disease, bone softening, chronic renal failure. However, both lead and aluminum are widely used in industrial applications and daily life. The limits of Pb²⁺ and Al³⁺ for drinking water according to the World Health Organization (WHO) standard are 0.5 and <sc>7.41 µmol/L</sc> respectively. Thus, it is necessary to develop real-time and rapid detection of Pb²⁺ and Al³⁺. Fluorescent probes are favored by researchers because of their high sensitivity and selectivity, rapid real-time monitoring and potential application in biological systems. The emission of the traditional panel-like chromophore is weakened or even quenched at high concentration or aggregation, while at low concentration, it exhibits low sensitivity and is easy to photobleaching. Tang and coworkers noticed that some luminogens with twisted conformations are nearly nonemssive in solution but exhibit boosted emission in aggregate states, thus, Tang coined this phenomenon as aggregation induced emission (AIE). With the disclosure of the AIE mechanism of restriction of motion (RIM), many AIE active luminogens have been developed. Some turn-on mode fluorescent sensors for Pb²⁺ and Al³⁺ have also been reported based on AIE mechanism, but few of them worked in pure water. Two water-soluble fluorescent sensors are constructed using phthalic acid structure as electron acceptor and tetraphenylethylene as core: 4,4′-(2,2-diphenylethene-1,1-diyl)diphthalic acid (<bold>1</bold>) and 4,4′-(2,2-bis(4-(dimethylamino)phenyl)ethene-1,1-diyl)diphthalic acid (<bold>2</bold>). Both <bold>1</bold> and <bold>2</bold> are nearly nonemissive in solution, but their solids are highly luminescent with quantum yield of 17.1% and 7.3%. Emission of <bold>1</bold> and <bold>2</bold> in water in the presence of KOH is turned on upon addition of Pb²⁺ or Al³⁺, while exhibit nearly no response to the addition of other metal ions, indicating the high selectivity for Pb²⁺ or Al³⁺. The detection limit of <bold>1</bold> and <bold>2</bold> towards Al³⁺ was estimated as 2 and <sc>0.17 µmol/L,</sc> which meets the limit for drinking water according to the WHO standard <sc>(7.41 µmol/L).</sc> Fluorescent intensities of <bold>1</bold> and <bold>2</bold> enhanced by Pb²⁺ and Al³⁺ are not much affected by the existence of the interfering ions. The exception is that the emission intensity of <bold>1</bold> can be greatly enhanced by Zn²⁺ when detecting Pb²⁺, which may afford the the construction for highly sensitive sensors for Pb²⁺ through combination of <bold>1</bold> and Zn²⁺. The average particles size of <bold>1</bold> and <bold>2</bold> in water solution are 36 and <sc>98 nm</sc> determined by dynamic light scattering (DLS) analysis, respectively. The average particles size of <bold>1</bold> increased to 707 and <sc>292 nm</sc> upon addition of Pb²⁺ and Al³⁺, respectively. And average particles size of <bold>2</bold> increased to 986 and <sc>906 nm</sc> upon addition of Pb²⁺ and Al³⁺. Thus the emission enhancement of <bold>1</bold> and <bold>2</bold> upon addition of Pb²⁺ and Al³⁺ should be caused by the aggregate formation. The emissions of the water solutions of <bold>1</bold> or 2 in the presence of Pb²⁺ or Al³⁺ were quenched upon addition of ethylenediaminetetraacetic acid disodium salt dihydrate (EDTA-2Na) due to the competing coordination of EDTA-2Na with metal ions.

A Mn(II)-Coordination Polymer: Treatment Activity on the Endometriosis and Mechanism Exploration

A novel coordination polymer containing Mn(II) ions as nodes was prepared by the hydrothermal method, and its chemical formula is {[Mn2(L)(hfpd)(H2O)]·1.75H2O}n (1) (L = 4,4′-bis(imidazol-1-yl)-biphenyl and H4hfpd = 4,4′-(hexafluoroisopropylidene)diphthalic acid). It was then used for evaluation the relationship with the Endometriosis (EMs). The activation for the estrogen receptor relative expression on the surface of endometrial cell was detected through the real time RT-PCR, and the results showed that complex 1 could obviously decreased the estrogen receptor over expression on the endometrial cell surface dose dependently. The immune function of the macrophages under the endometrial cells were determined by Western blot, the data indicated that complex 1 exerts the excellent treatment activity via activating the autophagy in macrophages. Molecular docking simulations reveal that the origin of the biological activity is from the carboxyl functional groups on the complex.

PDA-cross-linked beta-cyclodextrin: a novel adsorbent for the removal of BPA and cationic dyes.

In this study, 4,4'-(hexafluoroisopropene) diphthalic acid (PDA)-CD polymers containing β-cyclodextrin (CD) were synthesized for the adsorption of endocrine disrupting chemicals (EDCs) and dyes. It features great adsorption of bisphenol A (BPA), methylene blue (MB) and neutral red (NR). The maximum adsorption capacities of MB, NR and BPA can reach 113.06, 106.8 and 51.74 mg/g, respectively. The tandem adsorption results revealed that adsorptions of dyes and BPA onto PDA-CD polymer were two independent processes: non-polar BPA entrapment by cyclodextrin cavities while dyes were captured by the carboxyl groups and π-π stacking interactions. The adsorption processes performed well in a wide range of pH (4.0-10.0) and were not affected by fulvic acid (FA) and inorganic ions.

An unprecedented binodal (4,6)-connected Co(II) MOF as dual-responsive luminescent sensor for detection of acetylacetone and Hg2+ ions

A new Co(II) organic framework, {[Co2(L)(hfpd)(H2O)]·1.75H2O}n (1) (H4hfpd = 4,4′-(hexafluoroisopropylidene)diphthalic acid, L = 4,4′-bis(imidazol-1-yl)-biphenyl) was hydrothermally synthesized and characterized. 1 possesses an unusual (4,6)-connected layered network architecture. Fluorescence titration results present that 1 is rarely dual-responsive probe to detect acetylacetone and Hg2+ ions by luminescence quenching.

A 2D coordination polymer assembled from a nickel(II) tetraazamacrocyclic cation and 4,4'-(dimethylsilanediyl)diphthalate(3-) linker.

The preformed nickel(II) complex of the 14-membered macrocyclic ligand 1,4,8,11-tetraazacyclotetradecane (cyclam, L), when treated with 4,4'-(dimethylsilanediyl)diphthalic acid (H4A) in a DMF/H2O mixture (4:1 v/v) under heating, leads to [Ni(L)]3(HA)2·3DMF (I·DMF). Redissolution of this compound in a DMF/H2O/MeOH mixture (4:1:30 v/v/v) with mild acidification under gentle heating results in the formation of a similar compound but containing water and methanol molecules of crystallization, [Ni(L)]3(HA)2·5H2O·2MeOH (II·H2O). At lower temperature and concentration of reactants and longer reaction time, single crystals of composition {[{Ni(L)}3(HA)2]·4CH3OH}n (II·MeOH) were isolated. Single-crystal X-ray diffraction analysis of this compound, which, according to PXRD is isostructural with II·H2O but different from I·DMF, revealed its two-dimensional (2D) polymeric structure, i.e. poly[[bis{μ3-4-[(4-carboxy-3-carboxylatophenyl)dimethylsilyl]benzene-1,2-dicarboxylato-κ3O1:O2:O3'}tris(1,4,8,11-tetraazacyclotetradecane-κ4N)trinickel(II)] methanol tetrasolvate], {[Ni3(C18H13O8Si)2(C10H24N4)3]·4CH3OH}n. It is built up of the monoprotonated tricarboxylate HA3- ligand coordinated in a monodentate manner in the axial positions of two crystallographically independent NiII cations, one of which is located on a crystallographic inversion centre. Both metal ions adopt a slightly tetragonally elongated trans-N4O2 octahedral geometry. The compound has a lamellar structure with polymeric layers oriented parallel to the (10-2) plane, which are in turn linked via hydrogen bonds involving protonated carboxylic acid groups of the ligand. Bulk compounds I·DMF and II·H2O were characterized by FT-IR and diffuse reflectance spectroscopy and thermogravimetry, which provide evidence of their structural differences.

Synthesis, Crystal Structures, and Photocatalytic Activity of Two Nickel(II) Coordination Polymers with Flexible Bis(benzimidazol-1-yl)alkane and Polycarboxylate Ligands

Two ternary Ni(II) coordination polymers (CPs) named as: {[Ni2(L1)2(1,8-NDC)2(H2O)2]·2H2O}n (1), {[Ni2(L2)1.5(FA)(H2O)3]·3.75H2O}n (2), (L1 = 1,6-bis(5,6-dimethylbenzimidazol-1-yl)hexane, L2 = bis(5,6-dimethylbenzimidazol-1-yl)methane, 1,8-H2NDC = 1,8-naphthalenedicarboxylic acid, H4FA = 4,4′-(hexafluoroisopropylidene)diphthalic acid) were hydrothermally synthesized and characterized through physicochemical and spectroscopic methods. CP 1 features a 1D double straight-line chain and further extends into a 2D layers via π–π stacking interactions, while CP 2 shows a unique 2D (5,4,4)-connected network. The thermal stabilities, luminescence properties and photocatalytic activities of CPs 1–2 for methylene blue decomposition were also presented in detail. Two luminescent Ni(II) coordination polymers (CPs) were synthesized under hydrothermal condition. The crystal structure of CP 1 features a 1D double straight-line chain and further extends into a 2D layers via π–π stacking interactions, while CP 2 shows a unique 2D (5,4,4)-connected network. The photocatalytic experiments in the presence of catalysts CP 1 indicated higher degradation efficiency for MB solution than CP 2, and ·OH radical plays a key effect in the efficient degradation of MB.

An unusual (3,4,5)-connected 3D cadmium metal–organic framework as a luminescent sensor for detection of Cr2O72− in water

A metal-organic framework {[Cd2(L)(FA)(H2O)3]·H2O}n (1) was hydrothermal synthesized by utilizing a long flexible ligand 1,6-bis(benzimidazol-1-yl)hexane (L) and 4,4-(hexafluoroisopropylidene)diphthalic acid (H4FA). 1 possesses a unique (3,4,5)-connected 3D Cd(II)-organic framework with a point symbol of (42·62·72·84)(42·6)(64·82). Further, the luminescence explorations demonstrated that 1 exhibits sensitive sensing for Cr2O72− anion with high quenching efficiency Ksv value of 7.920 × 104 L·mol−1 and low detection limit (2.16 μM (S/N = 3)).

Synthesis and Characterization of 2D and 3D Zinc(II) Coordination Polymers with High Photocatalytic Activities for Removal of Methylene Blue Dye

Two zinc(II) coordination polymers (CPs) {[Zn2(L)(MIPA)2]·2H2O}n (1) and {[Zn(L)(H2FA)]·2H2O}n (2) were synthesized via hydrothermal reaction by employment the 5‐methylisophthalic acid (H2MIPA) or 4,4‐(hexafluoroisopropylidene)diphthalic acid (H4FA) and the flexible ligand 1,6‐bis(2‐methylbenzimidazol‐1‐yl)hexane (L). The CPs were characterized by physicochemical and spectroscopic methods as well as by single‐crystal X‐ray diffraction analysis. CP 1 possesses a rare 3D threefold interpenetration framework with coe topology, CP 2 displays a 2D corrugated network with a sql network with point symbol of (44·62). Both CPs exhibited high activities for the photocatalytic degradation of methylene blue in water. The photocatalytic mechanism was also investigated.

New Cd(II) and Zn(II) coordination polymers showing luminescent sensing for Fe(III) and photocatalytic degrading methylene blue

Hydrothermal reactions of the 1,5-bis(2-methylbenzimidazol-1-yl)pentane (L) and different polycarboxylates with cadmium(II)/zinc(II) acetate provided two new coordination polymers (CPs), namely, [Cd2(L)2(hfpd)]n (CP 1) and [Zn(L)(tbta)]n (CP 2) (H4hfpd = 4,4′-(hexafluoroisopropylidene)diphthalic acid, H2tbta = tetrabromoterephthalic acid). Both of the CPs were characterized by single crystal X-ray diffraction and elemental analysis, infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analyses. CP 1 possesses a two-dimensional (2D) 3,4L13 network with point symbol of {4·62}2{42·62·82}. CP 2 is a 3D sqc182 framework with the point symbol {66}. The solid-state ultraviolet emission by two CPs was quenched by Fe3+ in aqueous solution with detection limit 0.31 μM and 0.85 μM (S/N = 3) for CP 1 and CP 2, respectively. Further, CP 1 and CP 2 show promising photocatalytic activities for degradation of the methylene blue (MB) in water.

A New Three‐Dimensional Cd(II) Metal‐Organic Framework for Highly Selective Sensing of Fe3+ as well as Nitroaromatic Compounds

AbstractA new three‐dimensional Cd(II)‐organic framework [Cd(H2BDDA)]n based on fluorescent ligand, 4,4’‐([2, 2’‐bipyridine]‐6,6’‐diylbis(oxy) diphthalic acid(H4BDDA), has been successfully achieved. The obtained [Cd(H2BDDA)]n contained both fluorescent ligands and cadmium ions, thus showing multi‐responsive photoluminescence sensing properties. It can be used to detect Fe3+ with a sensitivity of 2.69 ppm in aqueous solution. For the fluorescence responses of [Cd(H2BDDA)]n dispersed in water solution with gradually increased p‐nitroaniline(p‐NA) and N‐methyl‐4‐nitroaniline (N−M‐4‐NA) concentrations, photoluminescence quenching can be detected even at a very low concentration of 0.68 ppm for p‐NA and 0.80 ppm for N−M‐4‐NA, which indicated that [Cd(H2BDDA)]n has an extremely high sensitivity to p‐NA and N−M‐4‐NA. To our best knowledge, [Cd(H2BDDA)]n is the first example of Cd(II) MOF based on the fluorescent ligand H4BDDA, which can be used for the detection of Fe3+ ions and NACs, especially for p‐NA and N−M‐4‐NA.

The One‐Stage Synthesis of Hyperbranched Polyimides by (A2+B4) Scheme in Catalytic Solvent

New tetraamine monomer bis(2,3‐diaminophenoxy)benzene (BDAPB) was synthesized by reducing corresponding precursor bis(2,3‐dinitrophenoxy)benzene with hydrazine hydrate. Hyperbranched polyimide with terminal amino groups was synthesized by means of the one‐stage high temperature polycondensation of BDAPB with 2,2‐propylidene‐(1,4‐phenyleneoxy)diphthalic acid in catalytically active solvent – molten benzoic acid at 140°C by the scheme A2+B4. Examples of polymer‐analog transformations were shown of terminal amino groups to form acetamide and phthalimide derivatives.

New examples of d10 metal–organic frameworks based on 4,4′-(hexafluoroisopropylidene)diphthalic acid: Synthesis, crystal structure and luminescence

Two novel coordination polymers, [Zn4(hfpd)2(phen)4(H2O)4]n (1), {[Cd2(hfpd)(bpy)(H2O)]·H2O}n (2) (phen=1,10-phenanthroline, bpy=4,4′-bipyridine, H4hfpd=4,4′-(hexafluoroisopropylidene) diphthalic acid), were synthesized and characterized by elemental analyses, FT-IR spectra, single-crystal X-ray diffraction analyses, TGA, powder XRD and fluorescent measurements. Compound 1 shows a 2D network structure built from tetranuclear zinc unit interconnected by (hfpd)4− ligands. The adjacent networks are further packed into 3D supramolecular structure through π⋯π interactions. 2 possess an unprecedented 3D structure containing 26-number circles and 1D parallelogram channels. Especially the (hfpd)4− ligands in 1–2 adopt three different conformations and coordination modes. In addition, the thermal stability and photoluminescence properties of 1–2 were also studied.

Complexation of Uranyl and Rare-Earth Ions by a Fluorinated Tetracarboxylate. Formation of a Layered Assembly and Three-Dimensional Frameworks

The reaction of uranyl and rare-earth nitrates with 4,4′-(1,1,1,3,3,3-hexafluoroisopropylidene)diphthalic acid (H4L) under hydro-/solvo-thermal conditions (2:1 water/acetonitrile at 180 °C) gives a series of complexes, most of which have been crystallographically characterized. In the lattice of the uranyl complex [(UO2)2(L)(H2O)2]·2H2O (1), the metal atoms are chelated by two adjacent carboxylate groups, each of the latter being bridging bidentate, and the resulting coordination polymer is two-dimensional. The ∼14 Å thick layers comprise two uranyl-covered faces linked to one another by L4– pillars, a claylike architecture likely due to the hydrophobic interactions between the organic ligands. The complexes [Ce(HL)(H2O)]·1.5H2O (2) and [Nd(HL)(H2O)]·2.5H2O (3) are isomorphous and they display a high degree of connectivity, with the metal atoms in ten- or eleven-coordinate environments being bound to five or six HL3– ligands. The three-dimensional (3D) framework formed contains one-dimensional subunits of adjacent metal ions with each coordination polyhedron sharing two triangular faces with its neighbors. The hydrophobic CF3 groups are oriented divergently from the exterior of wide channels (∼22 × 8 Å), which are occupied by the solvent water molecules. The complexes with rare-earth ions of smaller ionic radii, [M4(L)3(H2O)9]·7H2O with M = Er (4), Yb (5), and Y (6), are isomorphous to the previously reported terbium(III) complex, and they crystallize as 3D frameworks containing di- and tetra-nuclear subunits. In the visible region, only the uranyl and europium (and terbium) complexes display significant solid-state luminescence.

A Novel Coordination Polymer Based on 4,4'-(Hexauoroisopropylidene)diphthalic Acid: Synthesis, Structure and Physical Properties

The design and synthesis of coordination polymers is an attractive area of research, not only owing to their diverse topology and intriguing structures but also due to their potential applications in many fields, such as ion-exchange, catalysis, luminescence, magnets, and gas storage. The mainstream method of constructing such coordination polymers is to utilize organic ligands with aromatic polycarboxylate groups, because of their excellent coordination capability and flexible coordination patterns. Among them, aromatic polycarboxylic derivatives, such as 1,2,4,5-benzenetetracarboxylic acid, 4,4'-oxydiphthalic acid, 4,4'-(hexauoroisopropylidene)diphthalic acid (H4FA), and so on, have been extensively used to prepare coordination polymers. Meanwhile, the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (BTX) as an excellent derivative of triazole not only possesses the merits of triazole, but also can adopt different conformations compared with the corresponding 1,2,4-triazole ligand on the basis of the relative orientations of its CH2 groups. Taking these into consideration, we explored the self-assembly of Cd(II) ion, H4FA, and BTX under hydrothermal conditions, and obtained a novel 3D coordination polymer: [Cd3(BTX)2(HFA)2·2H2O]n. Herein, we report the synthesis, crystal structure, and physical properties.

3,3′-[Biphenyl-4,4′-diylbis(oxy)]diphthalic acid

In the title mol­ecule, C28H18O10, the two central benzene rings form a dihedral angle of 31.0 (1)°. In the phthalic acid fragments, the carb­oxy groups in the meta positions are approximately coplanar with the attached benzene rings, being inclined to their planes at 2.7 (1) and 10.3 (1)°, while the carb­oxy groups in the ortho positions are twisted from the benzene ring planes by 83.5 (1) and 75.4 (1)°. In the crystal, O—H⋯O hydrogen bonds link the mol­ecules into layers parallel to the bc plane. Weak C—H⋯O hydrogen bonds and π–π inter­actions between the aromatic rings [centroid–centroid distance = 3.7674 (3) Å] further consolidate the crystal packing.

A new three-dimensional terbium-carboxylate framework possessing Tb2 and Tb4 clusters: Synthesis, structure, luminescent and magnetic properties

Abstract A new three-dimensional terbium-carboxylate framework [Tb4L3(H2O)9]·7H2O (1) [(H4L = 4,4′-(hexafluoroisopropylidene)diphthalic acid)] has been hydrothermally synthesized and structurally characterized. The framework contains Tb2 and Tb4 clusters, and exhibits an unprecedented 4-nodal (3,4,5,8)-connected topology. In addition, the thermogravimetric analysis, luminescent and magnetic properties were investigated.

Zn(II) metal-organic frameworks (MOFs) assembled from semirigid multicarboxylate ligands: Synthesis, crystal structures, and luminescent properties

Two new coordination polymers [Zn 2L(2,2′-bpy)] n ∙(H 2O) 2 n ( 1) and [Zn 2L(phen)] n ∙(H 2O) 2 n ( 2) have been assembled from a semirigid multicarboxylate ligand 3,3′-(1,3-phenylenebis(oxy))diphthalic acid (H 4L) with the help of 2,2′-bipyridine (2,2′-bpy) or 1,10-phenanthroline (phen) as secondary ligand. Single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the space group C2/ c and displays a one-dimensional (1D) chain structure constructed from 2,2′-bpy and L ligand, which further forms a two-dimensional (2D) plane via intermolecular π–π interactions. Compound 2 belongs to the space group P 1 ¯ and features a 1D Δ- and Λ-typed chiral chain configuration despite the racemic nature for the whole complex. The neighboring chains with the same chirality are further stacked into a 2D ΔΔΔ- or ΛΛΛ-typed supramolecular structure via intermolecular π–π interactions because of the chiral recognition mechanism. Photophysical properties over complexes 1 and 2 have been comparatively investigated, revealing the effect of secondary ligand on the luminescent properties of these two complexes.

Four novel topological frameworks based on 4,4′-(hexafluoroisopropylidene)diphthalic acid and 1,1′-(1,4-butanediyl)bis(imidazole) ligand

Four new coordination polymers, constructed from 4,4′-(hexafluoroisopropylidene)diphthalic acid (H4L) and 1,1′-(1,4-butanediyl)bis(imidazole) (biim-4) ligand, have been synthesized: [Cd(HL)(Hbiim-4)(biim-4)0.5(H2O)]·2H2O (1), [Cd2(L)(biim-4)0.5(H2O)2]·0.5H2O (2), [Mn2(L)(biim-4)0.5(H2O)2]·0.5H2O (3), and [Zn2(L)(biim-4)1.5]·(CH3CH2OH) (4), where H4L = 4,4′-(hexafluoroisopropylidene)diphthalic acid, and biim-4 = 1,1′-(1,4-butanediyl)bis(imidazole). Compound 1 displays a 1D chain structure, which is extended by intermolecular hydrogen-bonding interactions to give a novel trinodal (4,5)-connected (4·64·8)(42·63·8)(43·64·83) topology. Compounds 2 and 3 are nearly isostructural with the same uncommon (5,6)-connected frameworks. Compound 4 shows an unprecedented self-penetrating (4,5)-connected net with Schlafli symbol of (42·6·72·8)(62·72·82)(42·63·73·82). The structural and topological differences of these four compounds indicate that the pH values and the central metals have significant effects on producing novel structures and topologies of the coordination complexes. The thermogravimetric and photoluminescent properties were also investigated for the compounds.