Elucidating the 2D Magnetic Topology of the ‘Metal–Radical’ TTTA⋅Cu(hfac)2 System

The TTTA ? Cu(hfac)₂ polymer ( 1 ; in which TTTA=1,3,5‐trithia‐2,4,6‐triazapentalenyl, and hfac=(1,1,1,5,5,5)‐hexafluoroacetylacetonate) is one of the most prominent examples of the rational use of the ‘metal–radical’ synthetic approach to achieve ferromagnetic interactions. Experimentally, the magnetic topology of 1 could not be fully deciphered. Herein, the first‐principles bottom‐up procedure was applied to elucidate the nature and strength of the magnetic J_AB exchange interactions present in 1 . The computed J_AB values give rise to a 2D magnetic topology of ferromagnetic dimers (+11.9 cm^?1) coupled through weaker antiferromagnetic interactions (?3.0 and ?3.2 cm^?1) in two different spatial directions. The hitherto unknown origin of the antiferromagnetic interdimer interactions is thus unveiled. By using the 2D magnetic topology, the agreement between calculated and experimental χT(T) data is extraordinary. In the metal–radical TTTA ? Cu(hfac)₂ compound, the computational model transcends the local dimer cluster model owing to strong interactions between metal centers and organic radicals, thereby creating a de facto biradical. In addition, it is shown that the magnetic topology cannot be inferred from the polymeric [TTTA ??? Cu(hfac)₂]_n crystal motif, that is, from its chemical coordination pattern. Instead, one should think in terms of magnetic building blocks, namely, the de facto biradicals.     

Synthesis,Characterizations, Magnetism and Thermal Degradation of a 2‐Fold Interpenetrated 3D Cobalt‐Organic Framework

A new coordination polymer, [Co₂(L)₂(4,4′‐bipy)]_n·3nH₂O ( 1 ) based on 5‐(3‐methyl‐5‐phenyl‐4H‐1,2,4‐triazol‐4‐yl)isophthalic acid (H₂ L ) and 4,4′‐bipyridine (4,4′‐bipy) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, XRPD, IR, and elemental analysis. Temperature‐dependent magnetic susceptibility and thermal degradation for 1 were also studied. The asymmetric unit of compound 1 consists of two crystallographically independent Co(II) ion, two L ^2? ligand, one 4,4′‐bipy ligand, and three lattice water molecules. The 2D triangle networks were linked by the bridging 4,4′‐bipy ligand to give rise to a 2‐fold interpenetrated 3D architecture. The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II) cations and three L ^2? ligands. So we can define Co(II) ions as 4‐connected nodes and the L ^2? ligands as 3‐connected nodes. Thus, the 3D structure can be described as a 2‐fold parallel interpenetrated ins InS 3,4‐conn topology.     

Heterometallic FeIII/K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature

The anionic Fe^III complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5‐Brthsa)₂] (5‐Brthsa‐H₂=5‐bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one‐step transition in heating mode and a two‐step transition in cooling mode. X‐ray structure analysis showed that the coexistence of hydrogen bond and cation–π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of Fe^II spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π–π stacking or hydrogen‐bond networks. As a consequence, the importance, or the very good suitability of alkali metal‐based coordination bonds and cation–π interactions for communicating cooperative interactions in spin‐crossover (SCO) compounds must be reconsidered.     

Zinc(II) and Cadmium(II) Metal Complexes with Bis(tetrazole) Ligands: Synthesis and Crystal Structures

Two new metal complexes [Zn( L¹ )]_n ( 1 ) and [Cd₃( L² )₂Cl₂(H2O)6]_n ( 2 ) (H₂ L¹ = 1,5‐bis(tetrazol‐5‐yl)‐3‐oxapentane, H₂ L² = bis(tetrazol‐5‐yl)methane) have been synthesized and characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction analysis. Complex 1 was a 2‐D sheet constructed by L¹ and Zn(II) center, further assembled to form a three‐dimensional (3‐D) supramolecular networks through weak hydrogen‐bonding interactions. In the complex 2 , there were two unequivalent Cd(II) centers, and some of ligands L² adopted chelate coordination mode, and others adopted bridge coordination mode linking the Cd1 center and simultaneously bridging the Cd2 center, the Cl^‐ anions adopted μ₂ bridging mode, ligands L² and the Cl^‐ anions linked the Cd(II) centers to form a 3‐D supramolecular networks.     

Bridging vinylalkylidene transition metal complexes

Vinylalkylidene transition metal complexes have been extensively used as ‘multitalent tools’ in organic synthesis, covering a broad field of applications. The vinylalkylidene ligands can be monodentate; alternatively they can adopt a bridging coordination mode in complexes with two adjacent metal atoms. As for other unsaturated organic ligands which can bond in both mono- and di-nuclear modes, the bridging coordination can give rise to new and different chemical properties from those found when the ligand is bound to a single metal centre. Likewise, the synthetic routes to bridging vinylalkylidene complexes offer a broader range of possibilities compared to those used to make mononuclear vinylalkylidenes. In spite of the fact that bridging vinylalkylidene complexes have been known for about 40 years, their synthetic potential as C₃ activated fragments has so far been under-exploited. Comparison with other C₃ bridged ligands (allenyls and allyls) indicates that vinylalkylidene ligands are reactive and versatile species. This review article gives an overview of the chemistry of bridging vinylalkylidene complexes to focus attention on their potential as synthetic tools.     

Acetate and malonate complexes of cobalt(II), nickel(II) and zinc(II) with hydrazinium cation

The hydrazinium(1+) metal acetates and malonate dihydrates of the molecular formula [(N₂H₅)₂M(CH₃COO)₄] and (N₂H₅)₂[M(OOCCH₂COO)₂(H₂O)₂] respectively, whereM=Co, Ni or Zn, have been prepared and characterized by chemical analyses, conductance, magnetic, spectral, thermal and X-ray powder diffraction studies. The magnetic moments and electronic spectra indicate that these complexes are of high-spin octahedral variety. The infrared spectra show that the hydrazinium ions are coordinated in the case of acetate complexes, whereas in the malonate complexes the hydrazinium ions are out side the coordination sphere. These complexes undergo exothermic decomposition in the temperature range 150–450°C to give the respective metal oxide as the final residue. The X-ray powder diffraction patterns of the malonate complexes indicate isomorphism among them.     

Synthesis,crystal structures and magnetic behaviors of two dicyanamide bridged di- and polynuclear complexes of cobalt(II) derived from 2,4,6-tris(2-pyridyl)1,3,5-triazine and imidazole

Two new dicyanamido-bridged di- and polynuclear complexes of Co(II), [Co(dca)(tptz)(H₂O)]₂·2(ClO₄) (1) and [Co(dca)₂(imz)₂]_n (2) [dca, dicyanamide; tptz, 2,4,6-tris(2-pyridyl)1,3,5-triazine; and imz, imidazole] have been synthesized and characterized structurally, as well as magnetically. The X-ray single crystal structure determination of complex 1 shows that two symmetry related octahedral Co(II) ions are separated by dca ligand and other coordination sites are satisfied by tptz and aquo ligands. Each dinuclear unit is associated with each other by intramolecular hydrogen bonding interactions, giving rise to a 1D chain structure. On the other hand complex 2 is a 1D coordination polymer having [Co(II)(imz)₂] units connected by double bridging dca ligands. These 1D chains interact through face-to-face π–π stacking interactions of the imz rings extending the dimensionality to a 2D supramolecular network. The variable temperature (300–2 K) magnetic measurements of both compounds reveal that dicyanamide exhibits a weak antiferromagnetic interaction between the metal centers.     

Complex Long-Range Magnetic Ordering Behaviors in Anisotropic Cobalt(II)–Azide Multilayer Systems

The crystal structures and magnetic properties of two new Co^II molecular magnets, [Co(N₃)₂(btzb)] ( 1 ) and [Co(N₃)₂(btze)₂] ( 2 ), are described and discussed (btzb=1,4-bis(tetrazol-1-yl)butane and btze=1,4-bis(tetrazol-1-yl)ethane). In the materials, (4,4) layers with μ-1,3-azide bridges are cross-linked by the monolayered btzb bridging ligands or spaced by bilayered btze terminal ligands to give a 3D ( 1 ) or 2D ( 2 ) coordination network with significantly different interlayer separations (10.6 vs. 15.2 Å). The observation that the layers in 1 and 2 are almost identical have not only allowed us to determine how the interlayer separation imposes its influences on their magnetic behavior, but also helps us understand the complex magnetic behavior of each structure. In the high-temperature range (>25 K), almost identical magnetic behaviors, typical of 2D antiferromagnetic systems, are observed for 1 and 2 . At low temperature they exhibit unusual and different behaviors that combine spin canting (weak ferromagnetism), metamagnetism, and stepped hysteresis. It has been found that the interlayer separation has little influence on the ordering temperature (23 vs. 22 K), but imposes very-strong influence on the metamagnetic critical field (6500 vs. 450 Oe), the coercivity (7500 vs. 650 Oe), and the hysteresis-step size. It may also play an adjusting role in determining the canting angle. Taking into account the strong anisotropy of the systems and the interlayer dipolar interactions, we have reasonably interpreted the unusual metamagnetic and hysteresis behaviors and the differences between 1 and 2 . In particularly, the stepped hysteresis loops have been explained by two weak ferromagnetic states.     

From low-dimensional manganese(II) azido motifs to higher-dimensional materials: structure and magnetic properties

Four new inorganic-organic hybrid coordination polymers in which 1D or 2D manganese(II) azido inorganic motifs are interlinked into higher-dimensional networks have been synthesized by use of a series of bis(pyridyl)-type organic bridging ligands (linkers) with different side groups and/or different coordination orientations. The dimensionality and the topology of the manganese(II) azido motif and the whole structure are sensitive to the organic linkers used. Compounds 1 and 3 are 3D coordination polymers with pillared-layer architectures: in 1, 2D Mn(II) layers with alternate double end-on (EO) and single end-to-end (EE) azido bridges are pillared by zigzag organic linkers, and 3 is built from single EE azido-bridged Mn(II) layers and linear organic linkers. The 3D nets of 1, 3, and related compounds have been related to the specific length and coordination orientation of the organic pillars and the undulate shape of the manganese(II) azido layers. Consistent with their structures, both 1 and 3 exhibit weak ferromagnetism due to spin canting. Compound 1 is a weak ferromagnet with T(c) = 16 K, and 3 is a metamagnet with T(c) = 23 K. On the other hand, compounds 2 and 4 are 2D coordination networks in which 1D manganese(II) azido chains are interlinked by organic linkers: 2 is the first 2D network built from Mn(II) chains with alternate double EE and double EO azido bridges, which mediate antiferro- and ferromagnetic interactions, respectively; 4 is the first 2D network built from Mn(II) chains with only single EE azido bridges, which mediate antiferromagnetic interactions. The magnetic susceptibility of 4 exhibits a rapid rise at very low temperature, which may be attributed to paramagnetic impurities or spin canting.     

Tuning the Formation of Cadmium(II) Urocanate Frameworks by Control of Reaction Conditions: Crystal Structure,Properties, and Theoretical Investigation

The reaction of cadmium(II) perchlorate with urocanic acid under different conditions created three novel coordination compounds: [Cd₂(L²)₂‐(L³)₂(H₂O)₈] ( 1 ), {[Cd(L)(L²)](H₂O)_1/2}_n ( 2 ), and {[Cd(L³)₂](H₂O)_3/2(EtOH)}_n ( 3 ), in which L, L², and L³ are three urocanate tautomers. Complex 1 consists of two separate mononuclear units with different urocanate tautomers, which self‐assemble into a 3D hydrogen‐bonding network constructed by alternating 2D layers, whereas complexes 2 and 3 self‐assemble into 3D alpha‐polonium and four‐fold interpenetrated diamondoid networks, respectively. The tautomerism of the urocanate ligands and the enormous structural diversity of their complexes are present in this system, which illustrates that the reaction temperature, pressure, and the metal ions themselves act cooperatively to tune the tautomerism of the ligands and the frameworks of their metal coordination compounds. The fluorescence‐emission and nitrogen‐adsorption properties of these complexes are also investigated.     

Synthesis,structures and electrochemical properties of two novel metal–organic coordination complexes based on trimesic acid (H3BTC) and 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (BPO)

Two novel metal–organic coordination complexes [Cu(HBTC)(BPO)]·H₂O (1) and [Co₃(BTC)₂(BPO)₃(H₂O)₂]·5.25H₂O (2), have been synthesized from hydrothermal reaction of metal chloride with the mixed ligands 1,3,5-benzenetricarboxylate (H₃BTC) and bent dipyridyl based ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (BPO), and structurally characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction analysis. The results reveal that each dinuclear Cu^II unit is bridged by two kinds of different ligands (H₃BTC and BPO) to form one-dimensional (1-D) chain structure in complex 1. The adjacent chains for 1 are further linked by π–π stacking interactions and hydrogen bonding interactions to form a three-dimensional (3-D) supramolecular framework. Complex 2 possesses a 3-D network composed of three different cobalt(II) centers [carboxylate-bridged dinuclear cobalt units and mononuclear cobalt ion] and bridging ligands BTC and BPO, which presents the first example of 3-D coordination polymer constructed from the BPO ligands simultaneously showing three different coordination modes. Moreover, the electrochemical behaviors of the two complexes bulk-modified carbon paste electrodes (1-CPE and 2-CPE) have been reported.     

Cluster-based Magnetic Porous Coordination Polymers

The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits： （1） nanoporous spin crossover materials with single metal nodes; （2） metal-radical approach with rigid organic radical ligands and single metal nodes; （C） PCPs with rigid organic ligands and metal oligomer nodes; （D） PCPs with metal complex linkers and polymetal cluster nodes; （E） PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious： the pore benefits from the big cluster according to ＂Scale Chemistry＂, and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.     

新型无机聚合物的设计合成、结构规律与性能研究*

本文以新型无机聚合物的合理合成和物理性能研究为主线, 总结3个系列具有新颖结构聚合物的组装与结构化学规律: (1)通过化学自组装法设计合成出系列金属-有机纳米笼、金属-有机纳米管和金属-有机纳米线.研究了合成金属-有机纳米分子的规律,开辟了一条合成金属-有机纳米分子的新途经.(2)通过结构调控、金属与桥联基元作用,把团簇单元活化后合成一维新型无机聚合物.在研究反应机理过程中分离和表征了大量的中间态产物,从而得到了这类聚合物合理合成的规律.(3)设计合成出二维层状(石墨型)、三维大孔(分子筛型)、金属聚硫及稀土与过渡金属混合4个系列新型的无机聚合物,总结了它们的结构规律和反应规律.在制备合成中既有结构单元自组装的反应又有设计合成的方法.通过系列化合物的结构表征和光、电或磁性能的研究, 探索出系列聚合物具有半导体性能和非线性光学性能,总结出聚合物的结构规律与基本结构单元组装的关系以及结构与性能的关系.     

Hydrothermal synthesis, crystal structures, and properties of Co and Ni supramolecular complexes with 2,4,6-trimethyl benzoate and 4,4′-bipyridyl

Two new coordination complexes, viz. [Co(tmb)₂(4,4′-bpy)₂(H₂O)₂](Htmb)₂ (1) and {[Ni(tmb)₂(μ-4,4′-bpy)₂(H₂O)₂](4,4′-bpy)}_n (2), have been hydrothermally synthesized by reaction of the corresponding metal acetate with 2,4,6-trimethylbenzoic acid (Htmb) and 4,4′-bipyridyl (4,4′-bpy). X-ray single-crystal diffraction suggests that complex 1 represents a discrete mononuclear species in which the central metal ion is coordinated by the terminal carboxylate moiety and the 4,4′-bipyridyl ligand. The crystal structure of complex 2 reveals a 1D chain coordination polymer in which the Ni(II) ions are connected by the bridging 4,4′-bipyridyl ligands. In both cases, the coordination arrays are further extended via hydrogen bonding interactions to generate 3D supramolecular networks. Complexes 1 and 2 have also been characterized by spectroscopic (IR and UV/Vis), thermal (TGA) and magnetic susceptibility measurements. In addition, both complexes exhibit antimicrobial activity.     

Two Unusual Two‐dimensional (4,4) Network Cadmium Coordination Polymers Based on Flexible Bis(triazole) and Rigid Benzenedicarboxylate Co‐ligands

Two cadmium(II) coordination polymers {[Cd(btp)(NO₂‐1,3‐bdc)(H₂O)]·H₂O}_n ( 1 ) and {[Cd(btp)(1,2‐bdc)(H₂O)]·H₂O}_n ( 2 ) were synthesized by the reaction of 1,3‐bis(1,2,4‐triazol‐1‐yl)propane (btp), 5‐nitroisophthalate (NO₂‐1,3‐bdc), and 1,2‐benzenedicarboxylate (1,2‐bdc). 1 consists of undulated 2D (4,4) networks. Two identical undulated layers are parallel stacking to give a (2D→2D) polythreaded 2D network. A 3D supramolecular architectute is constructed through the hydrogen bond interactions. 2 has an unusual 2D (4,4) network with a thickness of ca. 10 Å. The btp ligands exhibit the anti‐gauche conformation in 1 and the anti‐anti conformation in 2 . The flexible btp ligand exhibits the key role in the assembly of the topologies of 1 and 2 . The luminescence and thermal stability were investigated.     

Hybrid Coordination Networks Constructed from ɛ‐Keggin‐Type Polyoxometalates and Rigid Imidazole‐Based Bridging Ligands as New Carriers for Noble‐Metal Catalysts

Three hybrid coordination networks that were constructed from ?‐Keggin polyoxometalate building units and imidazole‐based bridging ligands were prepared under hydrothermal conditions, that is, H[(Hbimb)₂(bimb){Zn₄PMo^V8Mo^VI₄O₄₀}] ? 6 H₂O ( 1 ), [Zn(Hbimbp)(bimbp)₃{Zn₄PMo^V8Mo^VI₄O₄₀}] ? DMF ? 3.5 H₂O ( 2 ), and H[Zn₂(timb)₂(bimba)₂Cl₂{Zn₄PMo^V8Mo^VI₄O₄₀}] ? 7 H₂O ( 3 ) (bimb=1,4‐bis(1‐imidazolyl)benzene, bimbp=4,4′‐bis(imidazolyl)biphenyl, timb=1,3,5‐tris(1‐imidazolyl)benzene, bimba=3,5‐bis(1‐imidazolyl)benzenamine). All three compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single‐crystal X‐ray diffraction. The mixed valence of the Mo centers was analyzed by XPS spectroscopy and bond‐valence sum calculations. In all three compounds, the ?‐Keggin polyoxometalate (POM) units acted as nodes that were connected by rigid imidazole‐based bridging ligands to form hybrid coordination networks. In compound 1 , 1D zigzag chains extended to form a 3D supramolecular architecture through intermolecular hydrogen‐bonding interactions. Compound 2 consisted of 2D curved sheets, whilst compound 3 contained chiral 2D networks. Because of the intrinsic reducing properties of ?‐Keggin POM species, noble‐metal nanoparticles were loaded onto these POM‐based coordination networks. Thus, compounds 1 – 3 were successfully loaded with Ag nanoparticles, and the corresponding composite materials exhibited high catalytic activities for the reduction of 4‐nitrophenol.     

Synthesis,structures and magnetic properties of two 2D → 3D entangled Cobalt(II) coordination polymers

Two Co(II) coordination polymers, namely Co(HBTC)(4-bpdb)·H₂O (1) and Co(HBTC)(3-bpdb)·H₂O (2) (H₃BTC = 1,3,5-benzenetricarboxylic acid, 4-bpdb = 1,4-bis-(4-pyridyl)-2,3-diaza-1,3-butadiene, 3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3- butadiene), have been hydrothermally synthesized and characterized both structurally and magnetically. Compound 1 exhibits a (2D → 3D) polythreaded architecture. It is assembled from HBTC^2? ligands to form a 2D puckered (4,4) layer plus 4-bpdb ligands which are orientated above and below each layer. The structure of compound 2 consists of a 2D (3,5) wavelike sheet constructed from HBTC^2? anions and 3-bpdb spacers. The uncoordinated carboxyl groups of the HBTC^2? ligands protrude from both sides of the wavelike sheet to form a 2D → 3D interdigitated motif. The magnetic properties of both compounds are also investigated, indicating antiferromagnetic interactions between the adjacent metal centers.     

基于二-吡嗪-(2, 3-f: 2′3′-h)-喹喔啉和吡啶-2，5-二羧酸混合配体的两个新奇金属有机超分子骨架的水热合成、晶体结构与光致发光

以二-吡嗪-(2, 3-f: 2′3′-h)-喹喔啉(Dpq)和吡啶-2,5-二羧酸(2,5-H2pda)两种混合配体与不同金属硝酸盐为原料,通过水热反应得到了两个新奇的金属有机骨架[Zn2(Dpq)2(2,5-pda)2(H2O)2]·2H2O(1)和[Cd2(Dpq)2(2,5-pda)2]·2H2O(2),并经元素分析、TG、IR、X-射线单晶衍射分析进行了表征。结构分析表明,2,5-pda采取不同的配位方式桥连金属离子分别形成了二聚物1和2D菱形网络2。在化合物1中,相邻的二聚物通过氢键和π-π堆积作用形成扭曲的a-Po超分子结构。在化合物2中,相邻的配位聚合物层通过氢键拓展成扭曲的a-Po超分子骨架,而π-π堆积起到巩固骨架的作用。化合物1和2的结构差异表明了金属离子和配体在配位聚合物自组装过程中对结构的影响。此外固态标题化合物在室温下表现出蓝色的发光性质。     

Hydrothermal Synthesis and Structural Characterization of Two Zinc Coordination Polymers of 1,2‐Di(4‐pyridyl)ethylene and Benzenedicarboxylate

Hydrothermal reactions of Zn(NO3)2•6H2O with 1,2-di(4-pyridyl)ethylene (dpe) and 1,4-benzenedicarboxylate (1,4-BDC) or 1,3-benzenedicarboxylate (1,3-BDC) in water gave rise to two new metal-organic coordination polymers, [Zn(1,4-BDC)(dpe)]n (1) and [Zn4O(1,3-BDC)3(dpe)]n (2). Both compounds were characterized by elemental analysis and IR spectroscopy, and their structures were determined by single crystal X-ray diffraction. 1 displays a rare 5-fold interpenetrating 66-diamondoid framework while 2 possesses an interlocked 3D network formed by inclined interpenetration of 2D (4,4) networks that are constructed by μ4-oxo tetrazinc Zn4O cores and the bridging dpe and 1,3-BDC ligands. Thermal and photoluminescent properties of 1 and 2 were also investigated.     

Synthesis, structure, and characterization of three series of 3d-4f metal-organic frameworks based on rod-shaped and (6,3)-sheet metal carboxylate substructures

Three series of porous lanthanide metal-organic coordination polymers, namely [Cu(bpy)Ln(3)(ip)(5)(Hip)(H(2)O)] [Ln = Er (1a), Y (1b), Eu (1c); bpy = 2,2'-bipyridine, H(2)ip=isophthalic acid], [Cu(3)(bpy)(2)Ln(2)(ip)(6)(H(2)O)(5)] [Ln = Yb (2a), Gd (2b), Tb (2c)], and [Cu(3)Ln(2)(ip)(6)] [Ln = Eu (3a), Gd (3b)] have been synthesized hydrothermally by the reaction of the combination of 3d-4f metal centers and N-/O-donor ligands. X-ray diffraction analyses reveal that polymers 1a-c and 2a-c, as well as 3a, b are isomorphous in structure. Polymers 1a-c consist of 3D alpha-Po networks based on a inorganic rod-shaped secondary building units (SBUs) of {Er(6)Cu(2)(bipy)(2)(O(2)C)(11)} which are 27.03 A in length. Polymers 2a-c also contain 3D alpha-Po networks, constructed from shorter (14.79 A) but similarly rod-shaped SBUs of {Yb(2)Cu(3)(bpy)(2)(O(2)C)(12)}. The structure also contains hydrogen-bonded (H(2)O)(6) chains which can be reversibly dehydrated/rehydrated. Polymers 3a, b contain metal carboxylate substructures which have 2D (6,3) topologies; these layers are bridged by the ip(2-) ligands to give an overall 3D network which contains two sorts of cavities. This series of Ln-Cu coordination polymers are further characterized by antiferromagnetic behavior.