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In article number https://doi.org/10.1002/advs.201901855, Daofeng Sun, Hong‐Cai Zhou, and co‐workers report a series of zirconium metal–organic frameworks (MOFs) with intricate topologies mimicking inorganic minerals. The utilization of bent tetratopic linkers with various substituents uncovers new structural opportunities for Zr‐MOFs with sophisticated topologies for practical applications.

Successful encapsulation of phosphotungstic acid (PTA) within the nanocages of MIL-101 has been achieved via “ bottle around ship ” approach under static condition. XRD, FT-IR, 31 P MAS NMR, N 2 adsorption, SEM–EDS and XRF confirm the incorporation and well-distribution of PTA in both middle and large cavities of the MIL-101. SEM, XRD and TEM reveal the dominant crystal shapes of high loading PTA@MIL-101 are a monolithic and the adjacent lattice planes of MIL-101 are larger due to the addition of PTA. The host–guest composite materials PTA@MIL-101 containing 17–50 wt.% of PTA have been obtained and demonstrate an excellent catalytic performance in the oxidative desulfurization process of the refractory sulfur-containing compounds. This is the first example of the application of MIL-101 or PTA@MIL-101 composite materials in oxidative desulfurization. The reactivity of the sulfur-containing compounds follows the order DBT > 4,6-DMDBT > BT. In four consecutive reaction cycles, the catalyst recovery is in excess of 71%, while the DBT conversion slightly decreases.

Two amino-functional copper metal-organic frameworks of formula [Cu3(ATTCA)2(H2O)3]·2DMF·11H2O·12EtOH (1) (H3ATTCA = 2-amino-[1,1:3,1-terphenyl]-4,4,5-tricarboxylic acid, pyz = pyrazine, DMF = dimethylformamide) and [Cu3(ATTCA)2(pyz)(H2O)]·2DMF·12H2O·8EtOH (2) were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, infrared spectroscopy, elemental analyses, thermogravimetric analyses, and powder X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that both complexes 1 and 2 are built of the Cu2(COO)4 paddlewheel secondary building units with an fmj topology. Importantly, complex 1 can be transformed into complex 2 by the single-crystal to single-crystal transformation of which the coordinated water molecules are replaced with pyz molecules. However, the adsorption abilities of 2 are obviously lower than those of 1, as its pores are partially blocked by pyz molecules. Moreover, gas-adsorption analysis showed that the amino-functional 1 possesses higher gas-adsorption capacity than UMCM-151 for N2, H2, CH4, and C2H2, especially for CO2.

Hydrogen sulfide (H2S) has been considered as the third biologically gaseous messenger (gasotransmitter) after nitric oxide (NO) and carbon monoxide (CO). Fluorescent detection of H2S in living cells is very important to human health because it has been found that the abnormal levels of H2S in human body can cause Alzheimer’s disease, cancers and diabetes. Herein, we develop a cyclodextrin-based metal-organic nanotube, CD-MONT-2, possessing a {Pb14} metallamacrocycle for efficient detection of H2S. CD-MONT-2′ (the guest-free form of CD-MONT-2) exhibits turn-on detection of H2S with high selectivity and moderate sensitivity when the material was dissolved in DMSO solution. Significantly, CD-MONT-2′ can act as a fluorescent turn-on probe for highly selective detection of H2S in living cells. The sensing mechanism in the present work is based on the coordination of H2S as the auxochromic group to the central Pb(II) ion to enhance the fluorescence intensity, which is studied for the first time.

Crystallizations of tris(2-carboxyethyl)isocyanuric acid (H3tci) without or with N-heterocyclic organic molecules result in three distinct supramolecular complexes, [(H3tci)] (1), organic salt [(Hma)+·(H2tci)−] (2) and cocrystal [(H3tci)·(bipy)1.5] (3) (ma = melamine, bipy = 4,4′-bipyridine). In the absence of N-heterocyclic organic molecules, three 2-carboxyethyl arms of H3tci show a cisanti–cisanti–transanti conformation. The H3tci molecules are extended to a 2D 44-sql net via O–H⋯O hydrogen bonds. However, in the presence of ma or bipy, the conformation of the 2-carboxyethyl arms of H3tci in both 2 and 3 is transformed to cisanti–cisanti–cisgauche induced by cocrystallized N-heterocyclic organic molecules. In 2, ma plays a crucial role in the formation of O–H⋯N, N–H⋯O and O–H⋯O hydrogen bonds which direct the binary species to form the 2D double-layer structure containing 24-membered supramolecular macrocycles. Complex 3 is a 1D chain based on a [(H3tci)2·(bipy)2] 42-membered macrocycle incorporating the carboxyl–pyridyl H-bonding supramolecular synthons, which are extended by another bipy molecule to form the 1D chain. The 1D chains are further extended by means of a C–H⋯O non-classic hydrogen bond to form the resulting 2D layer containing three kinds of macrocycles. The 2D layers are packed into a 3D framework through π⋯π interaction between the triazinyl and pyridyl rings. Based on the structural analysis, we found that the conformation of H3tci could be modulated by introduction of the cocrystallized N-heterocyclic organic molecules. Moreover, the thermal stabilities of 2 and 3 are discussed.

Three lanthanide–organic frameworks have been solvothermally synthesized and characterized. Complex 1 {[Pr2(bbda)(OH)2(H2O)6]·12H2O}n (H4bbda = 5,5′-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(oxy)diisophthalic acid) is a 3D porous framework belonging to a 2-nodal net with the ssa topology. The coordinated formate ligand from in situ hydrolyzation of dmf binds metal centers to generate rigid rod-shaped SBUs (secondary building units) in both complexes 2 and 3, [Ln(HCOO)(L1)(dmf)]n (Ln = Er (2), Tm (3), H2L1 = 2,2′-(2,3,5,6-tetramethyl-1,4-phenylene) bis(methylene)bis(sulfanediyl)dibenzoic acid, dmf = N,N′-dimethylformamide). The flexible ligand H4bbda in complex 1 exhibits syn conformation, while the flexible ligand H2L1 in complexes 2 and 3 adopts anti conformation. The anti L1 ligand links the rod-shaped SBUs to give 2 and 3 3D network with the rtl topology.

Single-crystal-to-single-crystal (SCSC) transformations, which involve cooperative movement of atoms in the solid state, have received much attention from chemists. Through SCSC transformation, new complexes, which may not be obtained under conventional conditions, can be obtained in high yield. The SCSC transformation was first reported as a photoreaction in organic complexes, which could be considered as a new organic synthetic method. Solid-state photochemical [2+2] cycloadditions of organic molecules have been well studied. Recently, SCSC transformation has been extended to other complexes, such as metal complexes and coordination polymers (or metal–organic frameworks). In the past decades, many metal–organic frameworks (MOFs) that undergo SCSC transformation have been reported. Most of these reports describe the sliding of layers or breathing of 3D porous MOFs through solvent exchange. SCSC transformations involving breaking and forming bonds in the solid state remain quite rare. The MacGillivray and Foxman groups attained considerable success in solid-state photodimerization of organic groups mediated by metals. Converting a finite metal complex into an infinite coordination network was also reported by the groups of MacGillivray and Vittal. The reported topochemical dimerizations of metal complexes involve the organization of two double or triple bonds in the solid state: the geometric criteria are very important for such SCSC reactions. However, the coordination geometry of the metal ion remains unchanged in these topochemical dimerizations. More recently, zur Loye and co-workers described a 3D cobalt–organic framework exhibiting reversible shrinkage and expansion involving a change in the cobalt coordination geometry through SCSC transformation induced by the removal and re-absorption of guest molecules. Studies on the change in the metal coordination geometry caused by the removal and addition of ligands from the framework itself through SCSC transformation remain less common. Herein, we describe a new type of SCSC dimerization of a mononuclear copper complex, specifically, thermally induced head-to-tail dimerization involving the formation of a new Cu Oligand bond and a change in the metal coordination geometry. The transformation induced a color change from blue to green, which was caused by the change in the copper coordination geometry (Scheme 1). Interestingly, the trans

A new 2D lanthanide-organic framework with 1D rod-shaped SBUs based on 4,6-dimethyl-5-nitroisophthalic acid has been solvothermally synthesized. The uncoordinated 4,4′-bipy ligands, which are trapped in the cavities by forming weak offset face-to-face pyridine–phenyl interaction with the wall of the cavities, play a template role in the formation of the 2D layer. To the best of our knowledge, this is the first 2D lanthanide-organic framework that synthesized by templated synthesis.

To assemble metal-organic supramolecules such as a metallamacrocycle and metal-organic coordination cage (MOCC), a series of flexible dicarboxylate ligands with the appropriate angle, 2,2'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(1)), 2,2'-(2,5-dimethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(2)), 2,2'-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(sulfanediyl)dinicotinic acid (H(2)L(3)), and 2,2'-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H(2)L(4)), have been designed and synthesized. Using these flexible ligands to assemble with metal ions, six metal-organic supramolecules, Cd(2)(L(1))(2)(dmf)(4)(H(2)O)(2).H(2)O (1), Mn(3)((1)L(2))(2)((2)L(2))(dmf)(2)(H(2)O)(2).5dmf (2), Cu(4)(L(3))(4)(H(2)O)(4).3dmf (3), Cu(4)(L(4))(4)(dmf)(2)(EtOH)(2).8dmf.6H(2)O (4), Mn(4)(L(4))(4)(dmf)(4)(H(2)O)(4).6dmf.H(2)O (5), and Mn(3)(L(4))(3)(dmf)(4).2dmf.3H(2)O (6), possessing a rectangular macrocycle, MOCCs or their extensions, and 1D or 2D coordination polymers, have been isolated. All complexes have been characterized by single-crystal X-ray diffraction, elemental analysis, and thermogravimetric analysis. Complex 1 is a discrete rectangular macrocycle, while complex 2 is a 2D macrocycle-based coordination polymer in which the L(2) ligand adopts both syn and anti conformations. Complexes 3-5 are discrete MOCCs in which two binuclear metal clusters are engaged by four organic ligands. The different geometries of the secondary building units (SBUs) and the axial coordinated solvates on the SBUs result in their different symmetries. Complex 6 is a 1D coordination polymer, extended from a MOCC made up of two metal ions and three L(4) ligands. All of the flexible dicarboxylate ligands adopt a syn conformation except that in complex 2, indicating that the syn conformational ligand is helpful for the formation of a metallamacrocycle and a MOCC. The magnetic properties of complexes 5 and 6 have also been studied.

The solvothermal reaction of Nd(NO3)3·6H2O and 5-amino-2,4,6-triiodoisophthalic acid (H2atiip) in DMF/ethonal/H2O (5:2:1) in the presence of pyridine gave rise to a new open neodymium−organic framework having the NbO structure type, [Nd(HCOO)(atiip)(DMF)2]·DMF·H2O (1). Complex 1 can keep its diffraction pattern even after being heated to 200 °C.

Two 1D coordination polymers with a 1D zigzag and a helical chain, respectively, have been solvothermally synthesized. The different coordinated small molecules on the cadmium ion have significant influences on the formation of different architectures. Due to the existence of supramolecular interactions between the helices in complex 2, the same chirality is preserved, resulting in a chiral architecture. By introducing a chiral molecule as cosolute, the bulk homochiral crystallization from achiral precursors for 2 can be achieved.

Three metal-organic frameworks with 1D zigzag chain [Zn(dte)(H2O)3]·2H2O (1), 2D double layer [Cd(dtb)(H2O)(phen)] (2), 3D network [Zn(dte)(phen)] (3) based on tetrazole-based ligands (H2dtb = 1,3-dis(2H-tetrazol-5-yl)benzene, H2dte = 1,4-ditetrazolylethylene, phen = 1,10-phenanthroline), have been synthesized and characterized. All the compounds exhibit unusual strong luminescence at room temperature in the solid state and can be potentially used as luminescent materials.

Using ligands BITMB and IPA or TMIPA (BITMB = 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, IPA = isophthalic acid, TMIPA = 2,4,6-trimethylisophthalic acid), in which the BITMB can adopt syn or anti conformations, three metal−organic frameworks (MOFs) have been synthesized. These MOFs contain a variety of structures: a one-dimensional (1D) chain (1), two-dimensional (2D) interpenetrating layer (2), and three-dimensional (3D) porous framework (3). In MOFs 1 and 2, the BITMB ligand adopts a syn conformation, connecting metal ions to form a macrometallocycle or chain as the subunit, which are further connected by the rigid carboxylate ligands to generate the final 1D chain or 2D interpenetrating layer. The BITMB ligand in 3 adopts an anti conformation, which connects metal ions to form a 1D zigzag chain as the subunit. The 1D chain subunits are further connected by the carboxylate ligand to form the 3D porous framework. The conformation of the BITMB and thus the dimensionality of the MOF can be contro...

Self-assembly of Zn(NO3)2·6H2O, 5-amino-2,4,6-triiodoisophthalic acid (H2atiip) and 4,4′-bipyridine (bpy) or 1,3-di(4-pyridyl)propane (dpp) gave rise to three unusual zinc metal–organic frameworks, Zn2(bpy)2(atiip)2·3H2O·2dmf (1), Zn8(dpp)8(atiip)8·4H2O (2), Zn(dpp)(atiip)·(dmf)·(H2O) (3). All complexes possess 2D layer frameworks constructed from 1D Zn-carboxylate tubular unit for 1, 1D Zn-carboxylate helical chain for 2 and 3. In 1 and 2, the bpy or dpp act as both bridging and blocking ligands and the blocking ligands play an important role in the formation of the 2D layer frameworks. Both 2 and 3 contain two different large metallomacrocycles. Photoluminescence measurements of 1–3 in the solid state at room temperature show that all complexes exhibit luminescence, which can be assigned to an intraligand π → π∗ transition or ligand-to-metal charge transfer (LMCT).

Applying a nonplanar dicarboxylate ligand, a new 3D metal-organic framework, Zn(TBDC(1))(1/2)(TBDC(2))(1/2) (), possessing a rare (3,5)-connected net has been synthesized and characterized; complex can be formed from a 2D double layer by thermally liberating the coordinated water and dmf molecules, simultaneous with luminescence-increased changes.

A three-dimensional porous Zn metal-organic framework (UPC-12) with high thermal and chemical stability was isolated in high yield and purity from a hydrothermal reaction. UPC-12 exhibits high selectivity for CO2 due to the formation of hydrogen bonds between CO2 molecules and the -COOH groups exposed inside the channels and the effective π-π interactions between CO2 molecules and the pillared bipyridine moieties of the MOF. The adsorption-desorption process was studied, for the first time, by both (13)C CP-TOSS NMR spectroscopy and in situ DRIFTS.

The assembly of a fluorescent pentiptycene-based ligand with copper ion resulted in the formation of a 3D porous metal-organic framework (UPC-21) based on well-known paddlewheel SBUs. UPC-21 exhibits selective adsorption of CO2 over CH4 and N2 at 273 K and 295 K, C2H2 over CH4 at 273 K. The most significant performance of UPC-21 is its highly efficient detection of NACs such as 4-NP, 1,4-DNB, NB and 1,3-DNB with the calculated quenching constants, Ksv, being 3.097 × 106, 1.406 × 106, 4.420 × 105 and 1.498 × 105 M−1 for 4-NP, 1,4-DNB, NB, 1,3-DNB, respectively, which keeps a record on the fluorescence detection of NACs. This is the first porous Cu(II) MOF that exhibits fluorescent detection of NACs with high sensitivities.

Two 3D noninterpenetrating porous metal-organic frameworks (PMOFs) [Cd3(L(1))2(DMA)2]·DMA [1, H3L(1) = tris(p-carboxylic acid)tridurylborane] and [Zn3(L(2))3(H2O)2]·5H2O·2EtOH [2, H2L(2) = 4,4'-((2,3,5,6-tetramethylphenyl)boranediyl)bis(2,3,5,6-tetramethylbenzoic acid)] were synthesized by employment of a C3-symmetric ligand (H3L(1)) to assembly with Cd(NO3)2 or Zn(NO3)2. Complex 1 exhibits a (3, 6)-connected topological network based on a Cd3 cluster and Y-shaped trinodal organic linker. Complex 2 shows a 6-connected topology, since in situ decarboxylic reaction of the initial H3L(1) occurred to generate a new ligand, H2L(2), which can be considered as a linear linker. Both 1 and 2 exhibit blue fluorescence. Significantly, complex 1 with larger channels is unstable upon the removal of guest molecules. In contrast, activated 2 exhibits higher stability and permanent porosity.

Zinc paddlewheel metal-organic frameworks (MOFs) frequently exhibit low stability or complete collapse upon the removal of axial ligands. Hence, there are very few reports on gas adsorption of zinc paddlewheel MOFs. In this work, the N2 and H2 adsorption measurements were carried out for a zinc MOF (namely, SDU-1) based on two types of paddlewheel secondary building units (SBUs): [Zn2(COO)3] and [Zn2(COO)4]. Because of the existence of inherent surface instability upon removal of solvates in zinc paddlewheel SBU, SDU-1 possesses a very low surface area. Through metal-ion metathesis in a single-crystal-to-single-crystal fashion, the Zn(2+) ions in SDU-1 were exchanged by Cu(2+) ions to generate Cu-SDU-1. Through the measurements of gas adsorption and catalytic test, the porosity and catalytic capacity of Cu-SDU-1 have been improved significantly, compared to SDU-1.

A new porous zirconium metal–organic framework (Zr MOF), Zr6(μ3-O)4(μ3-OH)4(OH)6(H2O)6(BTB)2·6DMF·H2O (1; H3BTB = 5′-(4-carboxyphenyl)[1,1′:3′,1″-terphenyl]-4,4″-dicarboxylic acid), based on Zr6 clusters and tricarboxylate ligands has been constructed and characterized. The Zr6 clusters were linked by BTB ligands to generate a 2D network of kgd topology. The interpenetrations among the 2D networks gave rise to a 3D porous framework, which represents the first Zr MOF constructed from 2D → 3D interpenetration. The gas uptake and catalytic properties for 1 have also been studied.

By application of mixed organic ligands of 5-amino-2,4,6-triiodoisophthalic acid (H(2)ATIBDC) and 4,4'-bipyridine (bpy) to assemble with Zn ions at room temperature, two novel polymorphic structures, Zn(ATIBDC)(bpy).3H(2)O (denoted as MONT-1 and MONT-2), possessing one-dimensional metal-organic nanotubular structures have been synthesized and characterized. MONT-1 was generated by connection of the zero-dimensional Zn-bpy squares through the bridging ATIBDC ligands, while MONT-2 was formed by connection of the one-dimensional Zn-bpy helix through the ATIBDC ligands. Both nanotubes possess highly crystalline stabilities and can absorb the uncoordinated water molecules reversibly.

The self-assembly of flexible bended dicarboxylate ligand, 2,2′-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)-bis(sulfanediyl)-dibenzoic acid (H2L), with Mn(OAc)2·4H2O resulted in the formation of a novel metal–organic coordination cage with binuclear manganese SBU as the vertex, which represents the first metal–organic coordination cage constructed from a flexible dicarboxylate ligand and a binuclear SBU.

The solvothermal reaction of Zn(NO(3))(2)·6H(2)O and 4,4',4''-(2,4,6-trimethylbenzene-1,3,5-triyl)tribenzoic acid (H(3)TMTA) in N,N'-diethylformamide or N,N-dimethylacetamide gave rise to two layered honeycomb frameworks. The different stacking arrangements of the 2D layers generate achiral (α-1) and chiral (β-1) architectures, which are supramolecular isomers. The homochiral crystallization of β-1 can be achieved through chiral inducement, which is confirmed by circular dichroism spectra.

By application of a newly developed C(3)-symmetric tripodal carboxylate ligand, 1,1',1''-(benzene-1,3,5-triyl)tripiperidine-4-carboxylic acid (H(3)BTPCA) to assemble with zinc ion in the presence of pyridine, a novel 2-fold interpenetrating polyhedral metal-organic framework with a primitive cubic network based on supermolecular building blocks (SBBs) has been synthesized. The basic paddlewheel secondary building units (SBUs) are connected by deprotonated BTPCA ligands to generate an octahedron as the SBB, which is further connected through the six vertexes by sharing the paddlewheel SBUs to give rise to the 3D primitive cubic network.

A novel 1D metal−organic nanotube, exhibiting reversible and fast adsorption of the (H2O)12 cluster, has been synthesized and characterized.

Two porous metal–organic frameworks (1 and 2) with a fsc topology based on mixed ligands have been assembled and characterized. The different pillared ligands (pyrazine for 1 and 4,4′-bipyridine for 2) significantly influence the pore size of the frameworks. Gas uptake measurements reveal that complex 1 possesses higher H2, CO2, and CH4 uptake capacities than 2, although the surface area of 1 is lower than that of complex 2. These results further experimentally prove that the pore size plays an important role in gas uptake in porous MOFs, and the slit pore with a size of ~6 Å exhibits stronger interactions with gas molecules.

Three flexible bent dicarboxylate ligands, 2,2′-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(sulfanediyl)dibenzoic acid (H2L1), 2,2′-(1,4-phenylenebis(methylene))bis(sulfanediyl)dibenzoic acid (H2L9) and 2,2′-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(oxy)dibenzoic acid (H2L10), have been designed and synthesized. The positions of the functional substituents are in 1,4-positions of the central benzene ring, and all the ligands can adopt syn and anti conformations. By applying these flexible ligands to assemble with thulium ions or zinc ions, three metal–organic supramolecules with metallamacrocycles or 1D chains have been isolated. L1 adopts a syn conformation in complex 1, leading to a 0D metallamacrocycle, L9 in complex 2 adopts an anti conformation to form a 1D “rainbow-like” chain while L10 in complex 3 adopts both syn and anti conformations. L10 in a syn conformation connects Zn4(OH)2(CO2)4 SBU to form a 0D metallamacrocycle, which is further connected by the ligand in an anti conformation to generate a 1D coordination polymer.

Biphasic solvothermal reaction of Cu(NO3)2·6H2O and 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (H2TBDC) resulted in the formation of a novel coordination polymer, [Cu(TBDC)1/2]·H2O (BPS-1). BPS-1 possesses a 3D framework containing 1D Cu(I)–COO helical chains. The use of an organic solvent with a high boiling point and an extension of the reaction time play important roles in the reduction of Cu(II) ions to Cu(I) ions and the formation of BPS-1.

Three flexible dicarboxylate ligands 2,2′-(1,2-phenylenebis(methylene))bis(sulfanediyl)dibenzoic acid (H2L6), 2,2′-(2,4,6-trimethyl-1,3-phenylene)bis(methylene)bis(oxy)dibenzoic acid (H2L7) and 2,2′-(1,4-phenylenebis(methylene))bis-(sulfanediyl)dinicotinic acid (H2L8), have been designed and synthesized. All ligands can adopt syn or anti conformations and the positions of the functional substituents in the central benzene ring change gradually from 1,2-, 1,3- to 1,4-position. By applying these flexible ligands to assemble with copper ions, four metal–organic complexes based on paddlewheel SBU have been isolated. Complexes 1 and 2 are discrete molecular chairs. Complex 3 is a 1D molecular-chair-based coordination polymer. The molecular chairs, similar to that found in 1 and 2, are infinitely connected by the bridging 4,4′-bipy ligands to result in the formation of the 1D chain structure. Complex 4 is a two-dimensional wavelike layer structure containing a 68-member ring. Both L6 and L7 in 1 and 2 adopt syn conformation, while L8 adopts anti conformation, which results in the formation of the 2D layer structure of complex 4.

Three novel metal–organic frameworks, Cu4(OH)2(SO4)(HBTC)2(bpy)·bpy (1), Cu1.5(H2O)(TMBTC)(bpy)·1/2H2O (2) and Cd2(H2O)5(TMBTC)(bpy)2·NO3·3H2O (3), constructed from mixed organic ligands, have been synthesized and characterized. Complex 1 crystallizes in monoclinic space groupC2/c and possesses a 3D three-fold interpenetrating framework. The copper ions were first connected by HBTC and SO42− to generate a 1D ladder, which was further linked by a 4,4′-bipyridine ligand to give rise to a 3D interpenetrating framework. Complex 2 crystallizes in monoclinic space groupP2/c and possesses a 3D two-fold interpenetrating framework. Similar to 1, the copper ions were first connected by TMBTC to generate a 1D tubular unit, which can be considered as the assembly block. The 1D tubular unit was further linked by 4,4′-bipyridine ligands to result in the formation of the 3D framework. Complex 3 crystallizes in monoclinic space groupCc and has a three-dimensional structure. Different from 1 and 2, the cadmium ions were first connected by a 4,4′-bipyridine ligand to form a 1D chain as the assembly unit, which was further linked by TMBTC ligand to generate the final 3D framework. The photoluminescence measurement of 3 in the solid state at room temperature showed that complex 3 exhibits luminescence, which can be assigned to an intraligand π → π* transition.